WO2016039485A1 - Fiber-reinforced polyimide resin molded article and method for producing same - Google Patents

Fiber-reinforced polyimide resin molded article and method for producing same Download PDF

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Publication number
WO2016039485A1
WO2016039485A1 PCT/JP2015/076074 JP2015076074W WO2016039485A1 WO 2016039485 A1 WO2016039485 A1 WO 2016039485A1 JP 2015076074 W JP2015076074 W JP 2015076074W WO 2016039485 A1 WO2016039485 A1 WO 2016039485A1
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WIPO (PCT)
Prior art keywords
fiber
addition reaction
polyimide resin
reaction type
type polyimide
Prior art date
Application number
PCT/JP2015/076074
Other languages
French (fr)
Japanese (ja)
Inventor
渡辺　和伸
俊文 榎戸
幸太 瀬上
小林　祐介
Original Assignee
東洋製罐グループホールディングス株式会社
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Application filed by 東洋製罐グループホールディングス株式会社 filed Critical 東洋製罐グループホールディングス株式会社
Priority to EP15839594.7A priority Critical patent/EP3192827B1/en
Priority to US15/510,352 priority patent/US10406765B2/en
Priority to CN201580049233.3A priority patent/CN106715545B/en
Priority to BR112017004587-7A priority patent/BR112017004587B1/en
Publication of WO2016039485A1 publication Critical patent/WO2016039485A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28—Shaping operations therefor
    • B29C70/40—Shaping or impregnating by compression not applied
    • B29C70/42—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/002—Methods
    • B29B7/005—Methods for mixing in batches
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/02—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type
    • B29B7/22—Component parts, details or accessories; Auxiliary operations
    • B29B7/28—Component parts, details or accessories; Auxiliary operations for measuring, controlling or regulating, e.g. viscosity control
    • B29B7/286—Component parts, details or accessories; Auxiliary operations for measuring, controlling or regulating, e.g. viscosity control measuring properties of the mixture, e.g. temperature, density
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/88—Adding charges, i.e. additives
    • B29B7/90—Fillers or reinforcements, e.g. fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/02—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/06—Elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/82—Heating or cooling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2079/00—Use of polymers having nitrogen, with or without oxygen or carbon only, in the main chain, not provided for in groups B29K2061/00 - B29K2077/00, as moulding material
    • B29K2079/08—PI, i.e. polyimides or derivatives thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
    • B29K2105/12—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of short lengths, e.g. chopped filaments, staple fibres or bristles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

  • the present invention relates to a fiber-reinforced polyimide resin molded body and a method for producing the same. More specifically, the present invention has excellent sliding performance, and functional fibers in the polyimide resin are dispersed, so that shape stability during molding is achieved. The present invention relates to an excellent molded body and a method for producing the same.
  • molded products made of fiber reinforced resin made by blending functional fibers such as carbon fibers with resin have excellent properties such as weather resistance, mechanical strength, and durability.
  • the following Patent Document 1 describes a carbon fiber reinforced resin molded article composed of a specific pitch-based carbon short fiber mixture and a matrix resin, and describes that it is suitably used for various electronic components.
  • Patent Document 2 a friction material comprising a resin composition for a friction material using a specific aromatic polyimide oligomer as a binder such as carbon fiber has been proposed.
  • Patent Document 3 proposes a rolling element made of a carbon fiber reinforced synthetic resin containing 10 to 70% by weight of carbon fiber having a specific thermal conductivity.
  • an addition reaction type polyimide resin excellent in mechanical strength, heat resistance and durability and excellent in resin impregnation property As an addition reaction type polyimide resin, a highly functional addition reaction type polyimide resin capable of producing a carbon fiber reinforced composite by transfer molding (RTM) and resin injection (RI) has also been proposed (Patent Document 4).
  • the addition reaction type polyimide resin that can be suitably used as a matrix resin for functional fibers such as carbon fibers has a low melt viscosity in a prepolymer state.
  • an object of the present invention is to provide a fiber-reinforced polyimide resin molded article that has excellent sliding performance, is free from warpage, and has excellent shape stability during molding.
  • Another object of the present invention is to provide a production method capable of molding a fiber-reinforced polyimide resin molded article having excellent sliding performance with good shape stability.
  • a resin molded body in which functional fibers are dispersed in an addition-reaction type polyimide resin, which has a limit PV value of 3000 kPa ⁇ m / s or more. Is done.
  • the matrix of the composition constituting the resin molded body is an addition reaction type polyimide resin, and the functional fiber is impregnated with the polyimide resin, 2.
  • the functional fiber is contained in an amount of 5 to 200 parts by weight based on 100 parts by weight of the addition reaction type polyimide; 3.
  • the functional fiber is at least one of carbon fiber, glass fiber, aramid fiber, and metal fiber; 4).
  • the functional fiber is a carbon fiber having an average fiber length of 50 to 6000 ⁇ m and an average fiber diameter of 5 to 20 ⁇ m; 5. Containing a thickener in an amount of 5 to 40 parts by weight with respect to 100 parts by weight of the addition reaction type polyimide, and the thickener is dispersed in the resin molded body, 6).
  • the thickener is at least one of graphite, molybdenum disulfide, PTFE (tetrafluoroethylene resin), fine carbon-based material, and metal powder; Is preferred.
  • the prepolymer of the addition reaction type polyimide resin and the functional fiber are kneaded at a temperature not lower than the melting point (160 to 170 ° C.) of the addition reaction type polyimide resin and not higher than the thermosetting start temperature (near 300 ° C.).
  • a method for producing a resin molded body comprising at least a dispersion kneading step and a shaping step of shaping the mixture under a temperature condition equal to or higher than a thermosetting start temperature of an addition reaction type polyimide resin.
  • the kneaded product obtained in the dispersion kneading step is increased to increase the viscosity of the kneaded product by holding for a certain time at a temperature equal to or higher than the thermosetting start temperature of the addition reaction type polyimide resin. Having a viscous process, 2.
  • the functional fiber is contained in an amount of 5 to 200 parts by weight based on 100 parts by weight of the addition reaction type polyimide; 3.
  • the mixture obtained through the dispersion kneading step has a melt viscosity of 10 to 5000 Pa ⁇ s under a temperature condition of 300 to 320 ° C., the mixture is cooled, pulverized and mixed, and then pressure-shaped, 4). Adjusting the melt viscosity of the mixture at a temperature of 300 to 320 ° C. to 10 to 5000 Pa ⁇ s in the thickening step; 5.
  • the addition reaction type polyimide resin is a polyimide resin having a phenylethynyl group as an addition reaction group; 6).
  • the addition reaction type polyimide resin is a polyimide resin having a phenylethynyl group as an addition reaction group
  • the thickening step holding at a temperature of 310 ⁇ 10 ° C. for 30 to 60 minutes, Is preferred.
  • a method for producing a resin molded article comprising 5 to 200 parts by weight of functional fiber and 5 to 40 parts by weight of a thickener dispersed in 100 parts by weight of an addition reaction type polyimide.
  • a method for producing a resin molded body comprising: a shaping step of pressure-molding under a temperature condition equal to or higher than a thermosetting start temperature of an addition reaction type polyimide resin.
  • the melt viscosity under the temperature condition of 300 to 320 ° C. of the mixture after the dispersion kneading step is 10 to 5000 Pa ⁇ s.
  • the said shaping process is performed by compression molding.
  • an addition reaction type polyimide resin excellent in heat resistance, durability and mechanical strength is used as a matrix resin, and 5 functional fibers are added to 100 parts by weight of this addition reaction type polyimide.
  • 5 functional fibers are added to 100 parts by weight of this addition reaction type polyimide.
  • the functional fibers are uniformly cured and molded in the molded body, they are crosslinked and cured, so that they are free from warping and other distortion and can be suitably used as a slidable member.
  • the limit PV value is a value obtained by the product of the surface pressure P and the speed V when the frictional force suddenly increases.
  • the limit PV value is used as an index for determining whether the sliding member is suitable for the use environment. It is common to calculate. Under conditions close to the limit PV value, dynamic friction coefficient and sample temperature increase due to melting and seizure of resin due to frictional heat on the sliding surface, abnormal wear of the material, etc. are seen. Higher values indicate higher sliding performance. Means that.
  • the fiber-reinforced polyimide resin molded body of the present invention has a functional fiber impregnated with an addition-reactive polyimide and contains a predetermined amount of functional fiber, and is excellent in sliding and used as a sliding member. In addition to being able to maintain stable performance over a long period of time, deformation due to warpage can be prevented, so that productivity is excellent, and changes in PV value due to wear during long-term use can be reduced. Easy to manage devices.
  • the viscosity of the prepolymer (imide oligomer) of the polyimide resin in the molten state is added after the dispersion kneading step of the addition reaction type polyimide resin and the functional fiber.
  • the functional fiber in an amount of 5 to 200 parts by weight and the amount of 5 to 40 parts by weight with respect to 100 parts by weight of the addition reaction type polyimide.
  • the viscosity of the mixture after the dispersion kneading step is adjusted to a high viscosity of 10 to 5000 Pa ⁇ s under a temperature condition of 300 to 320 ° C. without providing a thickening step. It becomes possible to do.
  • the thickener suitably used in the present invention is excellent in slidability and can further improve the sliding performance.
  • the fiber-reinforced polyimide resin molded body of the present invention is a resin molded body in which functional fibers are dispersed in an addition reaction type polyimide resin described later, and it is important that the limit PV value is 3000 kPa ⁇ m / s or more. It has such features as heat resistance, durability, and mechanical strength, and has a large limit PV value and excellent sliding performance.
  • an addition reaction type polyimide resin is used as a polyimide resin to be a matrix of a composition constituting a fiber reinforced polyimide resin molded body.
  • the addition reaction type polyimide resin used in the present invention is composed of an aromatic polyimide oligomer having an addition reaction group at the terminal, and those prepared by a conventionally known production method can be used.
  • a method for the reaction a method of polymerizing at a temperature of 100 ° C. or lower, preferably 80 ° C.
  • a method comprising two steps of heat imidization by heating at a high temperature of about 140 to 270 ° C., or one step of performing a polymerization / imidization reaction at a high temperature of 140 to 270 ° C. for 0.1 to 50 hours from the beginning.
  • a method comprising two steps of heat imidization by heating at a high temperature of about 140 to 270 ° C., or one step of performing a polymerization / imidization reaction at a high temperature of 140 to 270 ° C. for 0.1 to 50 hours from the beginning.
  • the solvent used in these reactions is not limited to this, but N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, ⁇ -butyllactone, N- An organic polar solvent such as methylcaprolactam can be preferably used.
  • the terminal addition reaction group of the aromatic imide oligomer is not particularly limited as long as it is a group that undergoes a curing reaction (addition polymerization reaction) by heating when producing a resin molded body, but preferably performs a curing reaction.
  • a curing reaction addition polymerization reaction
  • any reactive group selected from the group consisting of a phenylethynyl group, an acetylene group, a nadic acid group, and a maleimide group is preferable.
  • the phenylethynyl group is suitable because it does not generate a gas component due to the curing reaction, and is excellent in the heat resistance and mechanical strength of the obtained resin molded body.
  • addition-reactive groups are a reaction in which a compound having an anhydride group or amino group together with an addition reactive group in the molecule forms an imide ring, preferably with an amino group or acid anhydride group at the terminal of an aromatic imide oligomer. Is introduced at the end of the aromatic imide oligomer.
  • Compounds having an anhydride group or amino group in the molecule together with an anhydride group or an amino group include, for example, 4- (2-phenylethynyl) phthalic anhydride, 4- (2-phenylethynyl) aniline, 4-ethynyl-phthalic anhydride, 4 -Ethynylaniline, nadic acid anhydride, maleic acid anhydride and the like can be preferably used.
  • Examples of the tetracarboxylic acid component that forms an aromatic imide oligomer having an addition reactive group at the terminal include 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyl At least selected from the group consisting of tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, and 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride
  • One tetracarboxylic dianhydride can be exemplified, and in particular, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride can be preferably used.
  • the diamine component that forms the aromatic imide oligomer having an addition reactive group at the terminal is not limited to this, but 1,4-diaminobenzene, 1,3-diaminobenzene, 1,2-diaminobenzene, 2,6- Diethyl-1,3-diaminobenzene, 4,6-diethyl-2-methyl-1,3-diaminobenzene, 3,5-diethyltoluene-2,4-diamine, 3,5-diethyltoluene-2,6- Diamine having one benzene ring such as diamine, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, 3,3′-diaminobenzophenone, 4,4′-diaminobenzophenone 4,4′-diaminodiphenylmethane, 3,3′-di
  • a mixed diamine composed of at least two aromatic diamines selected from the group consisting of methyl) benzidine, particularly 1,3-diaminobenzene and 1,3-bis (4-aminophenoxy) benzene.
  • the number of repeating units of the imide oligomer is preferably more than 0 and 20 or less, particularly 1 to 5, and is preferably in terms of styrene by GPC.
  • the number average molecular weight is preferably 10,000 or less, particularly 3000 or less.
  • Adjustment of the number of repeating units can be performed by changing the ratio of aromatic tetracarboxylic dianhydride, aromatic diamine, and compound having an anhydride group or amino group together with an addition reactive group in the molecule, By increasing the proportion of the compound having an anhydride group or amino group in the molecule and an anhydride group or amino group, the number of repeating units is reduced by lowering the molecular weight. The number of unit repetitions increases.
  • resin additives such as flame retardants, colorants, lubricants, heat stabilizers, light stabilizers, ultraviolet absorbers, fillers, etc.
  • flame retardants flame retardants
  • colorants colorants
  • lubricants heat stabilizers
  • light stabilizers light stabilizers
  • ultraviolet absorbers fillers, etc.
  • the functional fiber to be dispersed in the above-described addition reaction type polyimide resin conventionally known materials can be used, and conventionally known functionalities such as carbon fiber, aramid fiber, glass fiber, metal fiber, etc.
  • fibers can be used, carbon fibers can be particularly preferably used.
  • carbon fibers having an average fiber length of 50 to 6000 ⁇ m and an average fiber diameter of 5 to 20 ⁇ m can be preferably used.
  • the average fiber length is shorter than the above range, the effect of carbon fiber as a reinforcing material cannot be sufficiently obtained.
  • the average fiber length is longer than the above range, the dispersibility in the polyimide resin becomes poor. .
  • the handling property is inferior and expensive
  • the average fiber diameter is thicker than the above range
  • the settling rate of the functional fiber is increased and the functional fiber is increased. May tend to be unevenly distributed, and the strength of the fiber tends to decrease, and the effect as a reinforcing material may not be sufficiently obtained.
  • the content of the functional fiber has a significant influence on the sliding performance of the resin molded body and the occurrence of warpage during molding.
  • the functional fiber is added to 100 parts by weight of the addition reaction type polyimide. Containing 5 to 200 parts by weight, particularly 10 to 150 parts by weight, is suitable for obtaining a molded article having excellent sliding performance and excellent shape stability without warping. It is.
  • the limit PV value is less than the above value, and the slidability may be lowered.
  • the limit PV value may be lowered as compared with the case where the amount is within the above range. In addition, excessive thickening may occur and molding may not be possible.
  • inorganic materials such as fine carbon-based materials such as carbon black, metal powders such as aluminum powder and copper powder can be blended.
  • the inorganic material is preferably contained in an amount of 5 to 40 parts by weight with respect to 100 parts by weight of the addition reaction type polyimide.
  • the viscosity of the prepolymer of the addition reaction type polyamide resin is increased by using the thickener together with the functional fiber in an amount of 5 to 40 parts by weight with respect to 100 parts by weight of the addition reaction type polyimide.
  • the functional fibers can be maintained uniformly dispersed in the prepolymer without settling.
  • the thickener graphite, molybdenum disulfide, PTFE (tetrafluoroethylene resin), magnesium oxide, magnesium hydroxide, calcium hydroxide, and the like can be used. Among them, graphite, molybdenum disulfide, PTFE, The sliding performance can be further improved, which is particularly preferable.
  • the thickener is preferably contained in an amount of 5 to 40 parts by weight based on 100 parts by weight of the addition reaction type polyimide. If the amount of the thickener is less than the above range, the viscosity of the prepolymer does not increase sufficiently, the settling of the functional fibers cannot be sufficiently suppressed, and the warp deformation in which the functional fibers are uniformly dispersed It is not possible to mold a resin molded body without any. Further, if the amount of the thickener is larger than the above range, the sliding performance may be impaired, such as an increase in coefficient of friction and a decrease in wear resistance.
  • the first manufacturing method of the resin molded body of the present invention is at least a prepolymer (imide oligomer) of an addition reaction type polyimide resin and a functional fiber at a temperature not lower than the melting point of the addition reaction type polyimide resin and not higher than the thermosetting start temperature.
  • the viscosity of the kneaded product is maintained by holding the kneaded product obtained by the dispersion kneading step at a temperature equal to or higher than the thermal curing start temperature of the reactive polyimide resin for a certain period of time. It is characterized by having a thickening step (B) in which the viscosity of the kneaded product is adjusted to an appropriate range by raising the viscosity as necessary.
  • the addition reaction type polyimide resin used for molding the resin molded body of the present invention has a low viscosity in the state of the prepolymer before cross-linking and curing, and when functional fibers are contained, it settles. As a result, functional fibers are ubiquitous and warping occurs in the molded body.
  • the viscosity of the prepolymer is increased by the thickening step (B) to prevent sedimentation of the functional fiber, and the state thereof is changed. Since it is shaped in the shaping step (C) while being maintained, the functional fibers are uniformly dispersed, and it becomes possible to mold a molded product without warping by shrinking evenly during heat curing.
  • the prepolymer and the functional fiber are mixed by heating the prepolymer (imide oligomer) of the addition reaction type polyimide resin and the functional fiber at a temperature equal to or higher than the melting point of the addition reaction type polyimide resin and kneading while melting the prepolymer.
  • the functional fiber is used in an amount of 5 to 200 parts by weight, particularly 10 to 150 parts by weight, based on 100 parts by weight of the addition reaction type polyimide. Further, the above-mentioned inorganic materials can be blended in the above-mentioned amounts.
  • the above-mentioned thickener can be blended in the above-mentioned amount.
  • a conventionally known mixer such as a Henschel mixer, a tumbler mixer, or a ribbon blender can be used.
  • a batch type pressure kneader kneader
  • the present invention it is desirable to cool and solidify the mixture of prepolymer and functional fiber that has undergone the dispersion-kneading step, and then form a lump of a predetermined size. Thereby, it becomes possible to store the mixture in which the functional fibers are dispersed in the prepolymer with the lapse of time, and the handleability is also improved.
  • the melt viscosity of the mixture of the melt-kneaded prepolymer and the functional fiber under a temperature condition of 300 to 320 ° C. is 10 or less
  • the temperature of the polyimide resin used in the mixture is about 310 ⁇ 10 ° C. near the thermosetting start temperature.
  • the melt viscosity under the temperature condition of 300 to 320 ° C. is adjusted to the range of 10 to 5000 Pa ⁇ s. That is, when the mixture of the prepolymer and the functional fiber is held at a temperature of 310 ⁇ 10 ° C.
  • the prepolymer gradually starts to crosslink, so that the viscosity increases.
  • the functional fiber impregnated in the prepolymer by the dispersion kneading step can maintain a dispersed state without settling in the prepolymer due to this viscosity increase.
  • the reaction start temperature depends on the addition reaction group, and in the polyimide resin having a phenylethynyl group suitable as the addition reaction group in the present invention, 310 ⁇ 10 which is close to the thermosetting start temperature. It is desirable to heat at a temperature of 30 ° C. for 30 to 60 minutes.
  • the mixture of the prepolymer and the functional fiber whose melt viscosity is adjusted to the above range through the thickening step is shaped under a temperature condition equal to or higher than the thermosetting start temperature of the polyimide resin to be used as a resin molded body having a desired shape. Molded.
  • the mixture is cured by introducing a mixture of the polyimide prepolymer and functional fibers in the above-mentioned viscosity range in the molten state into a mold and heating and pressing at a temperature equal to or higher than the thermosetting start temperature.
  • the shaping is preferably performed by compression molding or transfer molding in which the mixture introduced into the molding die is compressed and compressed, but can also be molded by injection molding or extrusion molding.
  • the second production method of the resin molded body of the present invention is such that 5 to 200 parts by weight of functional fiber and 5 to 40 parts by weight of thickening agent are added to 100 parts by weight of the prepolymer (imide oligomer) of the addition reaction type polyimide resin.
  • a dispersion kneading step in which the agent is kneaded at a temperature not lower than the melting point of the addition reaction type polyimide resin and not higher than the thermosetting start temperature, and the mixture having undergone the dispersion kneading step is subjected to a temperature condition not lower than the thermosetting start temperature of the reaction type polyimide resin. It is characterized by comprising a shaping step for pressure shaping.
  • the addition reaction type polyimide resin used for molding the resin molded body of the present invention has a low viscosity in the state of the prepolymer before cross-linking and curing, and when functional fibers are contained, it settles. As a result, functional fibers are ubiquitous and warping occurs in the molded body.
  • the second production method of the present invention it is possible to increase the viscosity of the prepolymer without passing through the thickening step by adding a predetermined amount of thickener together with the functional fiber to the prepolymer. As a result, the functional fibers are dispersed without precipitating in the prepolymer, and the functional fibers are formed in the shaping process while maintaining the dispersed state. Thus, it becomes possible to mold a molded body without warping.
  • Prepolymer (imide oligomer) of addition reaction type polyimide resin, functional fiber, and thickener are heated at a temperature equal to or higher than the melting point of addition reaction type polyimide resin and kneaded while melting the prepolymer. Mix sex fibers.
  • the functional fiber is used in an amount of 5 to 200 parts by weight, particularly 10 to 150 parts by weight, and the thickener 5 to 40 parts by weight with respect to 100 parts by weight of the addition reaction type polyimide.
  • the kneading of the prepolymer and the functional fiber can be performed in the same manner as in the first production method described above.
  • the temperature of the dispersion kneading step is equal to or higher than the melting point of the prepolymer and equal to or lower than the crosslinking curing temperature, and particularly preferably, the mixture that has undergone the dispersion kneading step has a melt viscosity of 10 at a temperature of 300 to 320 ° C. It is preferably in the range of ⁇ 5000 Pa ⁇ s. The increase in viscosity and the penetration of the prepolymer into the functional fiber are combined, and the functional fiber does not settle and maintains a state dispersed in the prepolymer.
  • the mixture of the prepolymer, the functional fiber, and the thickener that has undergone the dispersion kneading step is cooled and solidified and then formed into a lump of a predetermined size. Thereby, it becomes possible to store the mixture in which the functional fibers are dispersed in the prepolymer with the lapse of time, and the handleability is also improved.
  • Warpage / Diameter ratio (%) t / D ⁇ 100 t: Test piece warpage (mm), D: Product diameter (mm)
  • the quality determination of the warp / diameter ratio was evaluated as ⁇ when less than 1.5% and ⁇ when 1.5% or more.
  • the melt viscosity at 310 ° C. was measured with a rheometer (ARES manufactured by TA instrument).
  • the measurement mode was dynamic frequency dispersion, the angular frequency was 0.1 to 500 rad / s, and the melt viscosity under the condition of 0.1 rad / s was taken as the measured value.
  • Example 1 11.1 parts by weight of pitch-based carbon fiber (K223HM manufactured by Mitsubishi Plastics) with an average single fiber length of 200 ⁇ m is blended with 100 parts by weight of addition-polymerized polyimide (PET-330 manufactured by Ube Industries Co., Ltd.). It was melt-kneaded at 280 ° C. for 30 minutes under atmospheric pressure. Then, the mixture (bulk molding compound, BMC) cooled to room temperature was obtained. The obtained BMC was divided into easy-to-handle sizes, held in an electric furnace at 310 ° C.
  • PTT-330 addition-polymerized polyimide
  • Example 2 42.9 parts by weight of pitch-based carbon fiber (K223HM, manufactured by Mitsubishi Plastics) with an average single fiber length of 200 ⁇ m is blended with 100 parts by weight of addition-polymerized polyimide (PET-330, manufactured by Ube Industries). It was melt-kneaded at 280 ° C. for 30 minutes under atmospheric pressure. Thereafter, BMC cooled to room temperature was obtained. After dividing the obtained BMC into a size that fits in the mold, the BMC was held in a mold for a compression molding machine at 280 ° C. to 320 ° C. for a certain period of time, and then melted and soaked. While applying pressure, the plate was heated to 371 ° C.
  • PKT-330 addition-polymerized polyimide
  • Example 3 The same as Example 2 except that the amount of carbon fiber was changed to 100 parts by weight.
  • Example 4 It was the same as Example 1 except that 310 ° C. was not maintained in the electric furnace. Since the obtained resin molding was warped, the front and back layers were scraped to a predetermined parallelism, and the limit PV value was measured. Although the limit PV value of the surface before cutting was not measured, when the measured surface was observed, carbon fibers were clearly present more than the surface before cutting. This also shows that a predetermined amount of carbon fiber is necessary on the surface.
  • Example 1 The same as Example 2 except that no carbon fiber was blended.
  • Example 2 It was the same as Example 2 except having changed the compounding quantity of carbon fiber into 233 weight part.
  • the viscosity of the BMC obtained after melt-kneading was high, and in some cases, the elongation in the mold was insufficient in the shaping process, and the limit PV value could not be measured.
  • Table 1 shows the results of measuring the limit PV values of the test pieces obtained in Examples 1 to 4 and Comparative Examples 1 and 2, the presence or absence of the thickening step, the quality of fiber dispersion, and the presence or absence of defects in the molded product.
  • Example 1 was the same as Example 1 except that BMC was set in an electric furnace at 310 ° C. for 45 minutes.
  • Example 6 Example 1 was the same as Example 1 except that BMC was changed to 310 ° C. for 60 minutes in an electric furnace.
  • Example 1 was the same as Example 1 except that BMC was changed to 310 ° C. for 15 minutes in an electric furnace. In addition, warpage deformation due to BMC leakage from the mold and non-uniform fiber distribution occurred.
  • Example 1 was the same as Example 1 except that BMC was changed to 310 ° C. for 75 minutes in an electric furnace. The resin viscosity was high and it could not be molded without stretching.
  • Table 2 shows the measurement results of the shapeability of the test pieces obtained in Examples 1, 5, 6 and Comparative Examples 3, 4, the quality of fiber dispersion, the warp / diameter ratio, and the melt viscosity.
  • Example 7 12.5 parts by weight of pitch-based carbon fiber (K223HM manufactured by Mitsubishi Plastics) with an average single fiber length of 200 ⁇ m, graphite powder (Wako Pure Chemical Industries) with respect to 100 parts by weight of addition polymerization type polyimide (PET-330 manufactured by Ube Industries) 070-01325) 12.5 parts by weight were blended and melt kneaded in a kneader at 280 ° C. under atmospheric pressure for 30 minutes. Then, the mixture (bulk molding compound, BMC) cooled to room temperature was obtained. After dividing the obtained BMC into a size that fits in the mold, the BMC was melted and soaked in a mold for a compression molding machine at 280 ° C. to 320 ° C.
  • BMC bulk molding compound
  • the plate was heated to 371 ° C. at a temperature rising rate of 3 ° C./min, held for 1 hour, and gradually cooled to obtain a plate having a diameter of 40 mm and a thickness of 3 mm.
  • the obtained plate was subjected to a curing treatment for 6 hours under the condition of 357 ° C., and then processed into a desired dimension to obtain a test piece.
  • Example 7 was the same as Example 7 except that the amount of carbon fiber was changed to 28.6 parts by weight and the amount of graphite powder was changed to 14.3 parts by weight.
  • Example 9 28.6 parts by weight of pitch-based carbon fiber (K223HM manufactured by Mitsubishi Plastics) with an average single fiber length of 200 ⁇ m, PTFE powder (manufactured by Kitamura Co., Ltd.) per 100 parts by weight of addition polymerization type polyimide (PET-330 manufactured by Ube Industries) (KT-600M) 14.3 parts by weight was blended and melt kneaded in a kneader at 280 ° C. under atmospheric pressure for 30 minutes. Thereafter, BMC cooled to room temperature was obtained. After dividing the obtained BMC into a size that fits in the mold, the BMC is melted and soaked in the mold for a compression molding machine at 280 ° C. to 320 ° C.
  • PTT-330 manufactured by Ube Industries
  • the plate was heated to 371 ° C. at a heating rate of 3 ° C./min, held for 1 hour, and gradually cooled to obtain a plate having a diameter of 200 mm and a thickness of 3 mm.
  • the obtained plate was subjected to a curing treatment for 6 hours under the condition of 357 ° C., and then processed into a desired dimension to obtain a test piece.
  • Example 9 was the same as Example 9 except that the amount of carbon fiber was changed to 14.3 parts by weight and the amount of PTFE powder was changed to 28.6 parts by weight.
  • Example 9 was the same as Example 9 except that the amount of carbon fiber was changed to 33.3 parts by weight and the amount of PTFE powder was changed to 33.3 parts by weight.
  • Table 3 shows the results of measurement of limit PV values of the test pieces obtained in Examples 4 and 7 to 11 and Comparative Example 5 and the quality of fiber dispersion.
  • FIG. 3 shows the fiber dispersion state in the test piece which was the same as that of Example 12 except for the plate thickness of 1.5 mm.
  • Example 12 Example 6 was the same as Example 6 except that the amount of carbon fiber was changed to 14.3 parts by weight and the amount of graphite powder was changed to 28.6 parts by weight.
  • Example 6 was the same as Example 6 except that the amount of carbon fiber was changed to 16.7 parts by weight and the amount of graphite powder was changed to 50.0 parts by weight.
  • Table 4 shows the measurement results of the formability of the test pieces obtained in Examples 4, 7 to 9, 12 and Comparative Example 6, the quality of fiber dispersion, the warp / diameter ratio, and the melt viscosity.
  • the state before applying the curing treatment for 6 hours under the condition of 357 ° C. is measured, and the quality is determined. It was.
  • the resin molded body of the present invention is excellent in sliding performance with a limit PV value of 3000 kPa ⁇ m / s or more, and therefore can be used for various applications as a sliding member in automobiles, electrical / electronic fields and the like.

Abstract

The present invention relates to a fiber-reinforced polyimide resin molded article and a method for producing same, and makes it possible to provide a molded article having a limit PV value of 3000 kPa·m/s or more, having excellent sliding performance, having a functional fiber dispersed in a polyimide resin, and having excellent shape stability during molding, by: dispersing and kneading an addition reaction-type polyimide resin prepolymer and a functional fiber; then increasing the viscosity of the kneaded product by holding the kneaded product for a fixed amount of time at a temperature at or above the heat curing start temperature of the reaction-type polyimide resin, or increasing the viscosity of the kneaded product by mixing in a thickening agent; and shaping the kneaded product in temperature conditions at or above the heat curing start temperature of the reaction-type polyimide resin.

Description

繊維強化ポリイミド樹脂成形体及びその製造方法Fiber-reinforced polyimide resin molded body and method for producing the same
　本発明は、繊維強化ポリイミド樹脂成形体及びその製造方法に関するものであり、より詳細には、優れた摺動性能を有すると共に、ポリイミド樹脂中の機能性繊維が分散し、成形時の形状安定性に優れた成形体及びその製造方法に関する。 The present invention relates to a fiber-reinforced polyimide resin molded body and a method for producing the same. More specifically, the present invention has excellent sliding performance, and functional fibers in the polyimide resin are dispersed, so that shape stability during molding is achieved. The present invention relates to an excellent molded body and a method for producing the same.
　従来より炭素繊維等の機能性繊維を樹脂に配合して成る繊維強化樹脂から成る成形体は、耐候性、機械的強度、耐久性等の特性に優れていることから、自動車、航空機等の輸送機材、土木・建設材料、スポーツ用品等の用途に広く使用されている。
　例えば、下記特許文献１には、特定のピッチ系炭素短繊維混合物及びマトリックス樹脂から成る炭素繊維強化樹脂成形体が記載されており、各種電子部品に好適に使用されることが記載されている。
　また下記特許文献２には、炭素繊維等のバインダーとして特定の芳香族ポリイミドオリゴマーを用いた摩擦材用樹脂組成物から成る摩擦材が提案されており、この摩擦材においては、従来、摩擦材のバインダーとして好適に使用されていたフェノール樹脂を用いた場合に比べて、バインダー自身の耐熱性や機械的特性が優れ、成形性が良好であることが記載されている。
　更に下記特許文献３には、特定の熱伝導率を有する炭素繊維を１０～７０重量％含む炭素繊維強化合成樹脂から成る転動体が提案されている。 Conventionally, molded products made of fiber reinforced resin made by blending functional fibers such as carbon fibers with resin have excellent properties such as weather resistance, mechanical strength, and durability. Widely used in equipment, civil engineering / construction materials, sports equipment, etc.
For example, the following Patent Document 1 describes a carbon fiber reinforced resin molded article composed of a specific pitch-based carbon short fiber mixture and a matrix resin, and describes that it is suitably used for various electronic components.
Further, in Patent Document 2 below, a friction material comprising a resin composition for a friction material using a specific aromatic polyimide oligomer as a binder such as carbon fiber has been proposed. It is described that the heat resistance and mechanical properties of the binder itself are excellent and the moldability is good as compared with the case of using a phenol resin that has been suitably used as the binder.
Further, Patent Document 3 below proposes a rolling element made of a carbon fiber reinforced synthetic resin containing 10 to 70% by weight of carbon fiber having a specific thermal conductivity.
　このような繊維強化樹脂成形体を軸受け等の摺動性部材として用いる場合には、強度、剛性等の機械的強度が高いこと、動摩擦係数が小さく摩耗量が少ないこと、更に限界ＰＶ値が高いこと等の特性が要求されており、機械的強度、耐熱性及び耐久性に優れ、また樹脂の含浸性に優れた付加反応型ポリイミド樹脂をマトリックス樹脂として用いることが望まれている。
　付加反応型ポリイミド樹脂として、トランスファー成形（ＲＴＭ）と樹脂圧入（ＲＩ）によって炭素繊維強化コンポジットを製造可能な高機能の付加反応型ポリイミド樹脂も提案されている（特許文献４）。 When such a fiber reinforced resin molded article is used as a slidable member such as a bearing, the mechanical strength such as strength and rigidity is high, the dynamic friction coefficient is small, the wear amount is small, and the limit PV value is high. Therefore, it is desired to use an addition reaction type polyimide resin excellent in mechanical strength, heat resistance and durability and excellent in resin impregnation property as a matrix resin.
As an addition reaction type polyimide resin, a highly functional addition reaction type polyimide resin capable of producing a carbon fiber reinforced composite by transfer molding (RTM) and resin injection (RI) has also been proposed (Patent Document 4).
特許第４５３８５０２号Patent No. 4538502 特開２００９－２４２６５６号公報JP 2009-242656 A 特開２０１１－１２７６３６号公報JP 2011-127636 A 特表２００３－５２６７０４号公報Special table 2003-526704 gazette
　しかしながら、繊維強化樹脂成形体のマトリックス樹脂として、付加反応型ポリイミド樹脂を用いる場合、優れた耐熱性、耐久性及び機械的強度が得られるとしても、得られた成形体に反りが生じてしまい、摺動性部材としては実用に供することができないという問題があった。
　本発明者等がこの原因について鋭意研究した結果、以下の事実が分かった。すなわち、炭素繊維等の機能性繊維のマトリックス樹脂として好適に使用できる付加反応型ポリイミド樹脂は、プレポリマーの状態で溶融粘度が低いことから、プレポリマーに機能性繊維を混合すると、機能性繊維が沈降してプレポリマー中に偏在した状態となり、この状態で樹脂が架橋硬化されることにより、機能性繊維の存在量に応じて成形体の収縮量に差が生じてしまい、得られる繊維強化樹脂成形体に反りを生じてしまうことが分かった。 However, when an addition reaction type polyimide resin is used as a matrix resin of a fiber reinforced resin molded body, even if excellent heat resistance, durability and mechanical strength can be obtained, the obtained molded body is warped, There was a problem that the slidable member could not be put to practical use.
As a result of intensive studies on this cause by the present inventors, the following facts were found. That is, the addition reaction type polyimide resin that can be suitably used as a matrix resin for functional fibers such as carbon fibers has a low melt viscosity in a prepolymer state. When the resin settles and becomes unevenly distributed in the prepolymer, and the resin is cross-linked and cured in this state, a difference occurs in the amount of shrinkage of the molded body depending on the amount of the functional fiber, and the resulting fiber-reinforced resin It was found that the molded body was warped.
　従って本発明の目的は、優れた摺動性能を有すると共に、反り等の発生がなく、成形時の形状安定性に優れた繊維強化ポリイミド樹脂成形体を提供することである。
　本発明の他の目的は、優れた摺動性能を有する繊維強化ポリイミド樹脂成形体を、形状安定性よく成形可能な製造方法を提供することである。 Accordingly, an object of the present invention is to provide a fiber-reinforced polyimide resin molded article that has excellent sliding performance, is free from warpage, and has excellent shape stability during molding.
Another object of the present invention is to provide a production method capable of molding a fiber-reinforced polyimide resin molded article having excellent sliding performance with good shape stability.
　本発明によれば、付加反応型ポリイミド樹脂中に機能性繊維が分散して成る樹脂成形体であって、限界ＰＶ値が３０００ｋＰａ・ｍ／ｓ以上であることを特徴とする樹脂成形体が提供される。
　本発明の樹脂成形体においては、
１.前記樹脂成形体を構成する組成物のマトリックスが付加反応型ポリイミド樹脂であり、前記機能性繊維に前記ポリイミド樹脂が含浸していること、
２．前記機能性繊維が、付加反応型ポリイミド１００重量部に対して５～２００重量部の量で含有されていること、
３．前記機能性繊維が、炭素繊維、ガラス繊維、アラミド繊維、金属繊維の何れか１種以上であること、
４．前記機能性繊維が、平均繊維長５０～６０００μｍ、平均繊維径５～２０μｍの炭素繊維であること、
５．前記付加反応型ポリイミド１００重量部に対して５～４０重量部の量の増粘剤を含有し、該増粘剤が前記樹脂成形体中に分散していること、
６．前記増粘剤が、グラファイト、二硫化モリブデン、ＰＴＦＥ（四フッ化エチレン樹脂）、微細炭素系材料、金属粉の少なくとも１種以上であること、
が好適である。 According to the present invention, there is provided a resin molded body in which functional fibers are dispersed in an addition-reaction type polyimide resin, which has a limit PV value of 3000 kPa · m / s or more. Is done.
In the resin molded product of the present invention,
1. The matrix of the composition constituting the resin molded body is an addition reaction type polyimide resin, and the functional fiber is impregnated with the polyimide resin,
2. The functional fiber is contained in an amount of 5 to 200 parts by weight based on 100 parts by weight of the addition reaction type polyimide;
3. The functional fiber is at least one of carbon fiber, glass fiber, aramid fiber, and metal fiber;
4). The functional fiber is a carbon fiber having an average fiber length of 50 to 6000 μm and an average fiber diameter of 5 to 20 μm;
5. Containing a thickener in an amount of 5 to 40 parts by weight with respect to 100 parts by weight of the addition reaction type polyimide, and the thickener is dispersed in the resin molded body,
6). The thickener is at least one of graphite, molybdenum disulfide, PTFE (tetrafluoroethylene resin), fine carbon-based material, and metal powder;
Is preferred.
　本発明によればまた、付加反応型ポリイミド樹脂のプレポリマーと機能性繊維を付加反応型ポリイミド樹脂の融点（１６０～１７０℃）以上、熱硬化開始温度（３００℃近傍）以下の温度で混練する分散混練工程、該混合物を付加反応型ポリイミド樹脂の熱硬化開始温度以上の温度条件下で賦形する賦形工程、を少なくとも有することを特徴とする樹脂成形体の製造方法が提供される。
　本発明の樹脂成形体の上記第一の製造方法においては、
１．前記分散混練工程と賦形工程の間に、分散混練工程で得られた混練物を付加反応型ポリイミド樹脂の熱硬化開始温度以上の温度で一定時間保持することにより混練物の粘度を上昇させる増粘工程を有すること、
２．前記機能性繊維が、付加反応型ポリイミド１００重量部に対して５～２００重量部の量で含有されていること、
３．前記分散混練工程を経て得られた混合物の３００～３２０℃の温度条件下における溶融粘度が１０～５０００Ｐａ・ｓであり、該混合物を冷却し粉砕混合した後、加圧賦形すること、
４．前記増粘工程において、混合物の３００～３２０℃の温度条件下における溶融粘度を１０～５０００Ｐａ・ｓに調整すること、
５．前記付加反応型ポリイミド樹脂が、付加反応基としてフェニルエチニル基を有するポリイミド樹脂であること、
６．前記付加反応型ポリイミド樹脂が、付加反応基としてフェニルエチニル基を有するポリイミド樹脂である場合には、前記増粘工程おいて、３１０±１０℃の温度で３０～６０分間保持すること、
が好適である。 According to the present invention, the prepolymer of the addition reaction type polyimide resin and the functional fiber are kneaded at a temperature not lower than the melting point (160 to 170 ° C.) of the addition reaction type polyimide resin and not higher than the thermosetting start temperature (near 300 ° C.). There is provided a method for producing a resin molded body comprising at least a dispersion kneading step and a shaping step of shaping the mixture under a temperature condition equal to or higher than a thermosetting start temperature of an addition reaction type polyimide resin.
In the first production method of the resin molded body of the present invention,
1. Between the dispersion kneading step and the shaping step, the kneaded product obtained in the dispersion kneading step is increased to increase the viscosity of the kneaded product by holding for a certain time at a temperature equal to or higher than the thermosetting start temperature of the addition reaction type polyimide resin. Having a viscous process,
2. The functional fiber is contained in an amount of 5 to 200 parts by weight based on 100 parts by weight of the addition reaction type polyimide;
3. The mixture obtained through the dispersion kneading step has a melt viscosity of 10 to 5000 Pa · s under a temperature condition of 300 to 320 ° C., the mixture is cooled, pulverized and mixed, and then pressure-shaped,
4). Adjusting the melt viscosity of the mixture at a temperature of 300 to 320 ° C. to 10 to 5000 Pa · s in the thickening step;
5. The addition reaction type polyimide resin is a polyimide resin having a phenylethynyl group as an addition reaction group;
6). When the addition reaction type polyimide resin is a polyimide resin having a phenylethynyl group as an addition reaction group, in the thickening step, holding at a temperature of 310 ± 10 ° C. for 30 to 60 minutes,
Is preferred.
　本発明によればまた、付加反応型ポリイミド１００重量部に対して、５～２００重量部の機能性繊維、５～４０重量部の増粘剤が分散して成る樹脂成形体の製造方法であって、前記付加反応型ポリイミド樹脂のプレポリマー、機能性繊維及び増粘剤を付加反応型ポリイミド樹脂の融点以上、熱硬化開始温度以下の温度で混練する分散混練工程、該分散混練工程を経た混合物を付加反応型ポリイミド樹脂の熱硬化開始温度以上の温度条件下で加圧賦形する賦形工程、とから成ることを特徴とする樹脂成形体の製造方法が提供される。
　本発明の樹脂成形体の上記第二の製造方法においては、前記分散混練工程を経た混合物の３００～３２０℃の温度条件下における溶融粘度が１０～５０００Ｐａ・ｓであることが好適である。
　また本発明の樹脂成形体の製造方法においては、前記賦形工程が、圧縮成形により行われることが好適である。 According to the present invention, there is also provided a method for producing a resin molded article comprising 5 to 200 parts by weight of functional fiber and 5 to 40 parts by weight of a thickener dispersed in 100 parts by weight of an addition reaction type polyimide. A dispersion kneading step of kneading the prepolymer of the addition reaction type polyimide resin, the functional fiber and the thickener at a temperature not lower than the melting point of the addition reaction type polyimide resin and not higher than the thermosetting start temperature, and the mixture obtained through the dispersion kneading step. There is provided a method for producing a resin molded body comprising: a shaping step of pressure-molding under a temperature condition equal to or higher than a thermosetting start temperature of an addition reaction type polyimide resin.
In the second production method of the resin molded body of the present invention, it is preferable that the melt viscosity under the temperature condition of 300 to 320 ° C. of the mixture after the dispersion kneading step is 10 to 5000 Pa · s.
Moreover, in the manufacturing method of the resin molding of this invention, it is suitable that the said shaping process is performed by compression molding.
　本発明の繊維強化ポリイミド樹脂成形体においては、耐熱性、耐久性及び機械的強度に優れた付加反応型ポリイミド樹脂をマトリックス樹脂とし、この付加反応型ポリイミド１００重量部に対して機能性繊維を５～２００重量部の量で配合することにより、限界ＰＶ値が３０００ｋＰａ・ｍ／ｓ以上と優れた摺動性能を発現することが可能になる。しかも成形体中に機能性繊維が均一に分散された状態で架橋硬化されて成形されていることから、反り等のゆがみがなく、摺動性部材として好適に使用できる。尚、限界ＰＶ値とは、摩擦力が急激に上昇するときの面圧Ｐと速度Ｖの積で求まる値であり、摺動部材として使用環境に適しているかを判断する指標として限界ＰＶ値を算出することが一般的である。限界ＰＶ値に近い条件下では摺動面の摩擦熱による樹脂の溶融・焼きつきによる動摩擦係数および試料温度の上昇、材料の異常摩耗などがみられ、この値が高いことは摺動性能が高いことを意味する。また本発明の繊維強化ポリイミド樹脂成形体は、機能性繊維に付加反応型ポリイミドが含浸し、かつ、機能性繊維を所定量に含有しており、摺動に優れ、摺動部材として用いた場合に、長期に亘って安定した性能を維持することができるばかりか、そりによる変形を防止できるので、生産性に優れるとともに、長期間使用時の磨耗によるＰＶ値の変化を小さくでき、交換時期や装置などの管理がしやすい。 In the fiber-reinforced polyimide resin molded article of the present invention, an addition reaction type polyimide resin excellent in heat resistance, durability and mechanical strength is used as a matrix resin, and 5 functional fibers are added to 100 parts by weight of this addition reaction type polyimide. By blending in an amount of ˜200 parts by weight, it becomes possible to develop excellent sliding performance with a limit PV value of 3000 kPa · m / s or more. In addition, since the functional fibers are uniformly cured and molded in the molded body, they are crosslinked and cured, so that they are free from warping and other distortion and can be suitably used as a slidable member. The limit PV value is a value obtained by the product of the surface pressure P and the speed V when the frictional force suddenly increases. The limit PV value is used as an index for determining whether the sliding member is suitable for the use environment. It is common to calculate. Under conditions close to the limit PV value, dynamic friction coefficient and sample temperature increase due to melting and seizure of resin due to frictional heat on the sliding surface, abnormal wear of the material, etc. are seen. Higher values indicate higher sliding performance. Means that. In addition, the fiber-reinforced polyimide resin molded body of the present invention has a functional fiber impregnated with an addition-reactive polyimide and contains a predetermined amount of functional fiber, and is excellent in sliding and used as a sliding member. In addition to being able to maintain stable performance over a long period of time, deformation due to warpage can be prevented, so that productivity is excellent, and changes in PV value due to wear during long-term use can be reduced. Easy to manage devices.
　また本発明の繊維強化ポリイミド樹脂成形体の第一の製造方法においては、付加反応型ポリイミド樹脂と機能性繊維の分散混練工程後に、溶融状態にあるポリイミド樹脂のプレポリマー（イミドオリゴマー）の粘度を増大させる増粘工程を設けることにより、プレポリマー中に機能性繊維が均一に分散した状態を維持することが可能になり、機能性繊維が沈降して偏在することがなく均一に分散した繊維強化ポリイミド樹脂成形体を反り変形を生じることなく成形することが可能になる。 In the first production method of the fiber-reinforced polyimide resin molded body of the present invention, the viscosity of the prepolymer (imide oligomer) of the polyimide resin in the molten state is added after the dispersion kneading step of the addition reaction type polyimide resin and the functional fiber. By providing a thickening step to increase, it becomes possible to maintain a state in which the functional fibers are uniformly dispersed in the prepolymer, and the functional fibers are uniformly dispersed without being settled and unevenly distributed. It becomes possible to mold the polyimide resin molded body without causing warp deformation.
　更に本発明の繊維強化ポリイミド樹脂成形体の第二の製造方法おいては、付加反応型ポリイミド１００重量部に対して、５～２００重量部の量の機能性繊維及び５～４０重量部の量の増粘剤が配合されていることにより、増粘工程を設けることなく、分散混練工程後の混合物の３００～３２０℃の温度条件下での溶融粘度を１０～５０００Ｐａ・ｓと高粘度に調整することが可能になる。これにより、プレポリマー中に機能性繊維が均一に分散した状態を維持することが可能になり、機能性繊維が均一に分散した繊維強化ポリイミド樹脂成形体を反り変形を生じることなく成形することが可能になる。
　また後述するように本発明で好適に用いる増粘剤は摺動性にも優れており、摺動性能を更に向上することができる。 Furthermore, in the second method for producing the fiber-reinforced polyimide resin molded body of the present invention, the functional fiber in an amount of 5 to 200 parts by weight and the amount of 5 to 40 parts by weight with respect to 100 parts by weight of the addition reaction type polyimide. The viscosity of the mixture after the dispersion kneading step is adjusted to a high viscosity of 10 to 5000 Pa · s under a temperature condition of 300 to 320 ° C. without providing a thickening step. It becomes possible to do. This makes it possible to maintain a state in which the functional fibers are uniformly dispersed in the prepolymer, and to form a fiber-reinforced polyimide resin molded body in which the functional fibers are uniformly dispersed without causing warp deformation. It becomes possible.
Further, as will be described later, the thickener suitably used in the present invention is excellent in slidability and can further improve the sliding performance.
実施例における限界ＰＶ値の測定方法を説明するための図である。It is a figure for demonstrating the measuring method of the limit PV value in an Example. 実施例における反り量の測定方法を説明するための図である。It is a figure for demonstrating the measuring method of the curvature amount in an Example. 繊維の偏在による繊維不均一性を示すための図である。It is a figure for showing the fiber nonuniformity by the uneven distribution of a fiber.
(樹脂成形体）
　本発明の繊維強化ポリイミド樹脂成形体は、後述する付加反応型ポリイミド樹脂中に機能性繊維が分散して成る樹脂成形体であって、限界ＰＶ値が３０００ｋＰａ・ｍ／ｓ以上であることが重要な特徴であり、耐熱性、耐久性及び機械的強度を有すると共に、限界ＰＶ値が大きく、優れた摺動性能を有している。 (Resin molding)
The fiber-reinforced polyimide resin molded body of the present invention is a resin molded body in which functional fibers are dispersed in an addition reaction type polyimide resin described later, and it is important that the limit PV value is 3000 kPa · m / s or more. It has such features as heat resistance, durability, and mechanical strength, and has a large limit PV value and excellent sliding performance.
[付加反応型ポリイミド樹脂]
　本発明においては、繊維強化ポリイミド樹脂成形体を構成する組成物のマトリックスとなるポリイミド樹脂として、付加反応型ポリイミド樹脂を用いることが重要な特徴である。
　本発明に用いる付加反応型ポリイミド樹脂は、末端に付加反応基を有する芳香族ポリイミドオリゴマーから成り、従来公知の製法により調製したものを使用することができる。例えば、芳香族テトラカルボン酸二無水物、芳香族ジアミン、及び分子内に付加反応基と共に無水物基又はアミノ基を有する化合物を、各酸基の当量の合計と各アミノ基の合計とをほぼ等量となるように使用して、好適には溶媒中で反応させることによって容易に得ることができる。反応の方法としては、１００℃以下、好適には８０℃以下の温度で、０．１～５０時間重合してアミド酸結合を有するオリゴマーを生成し、次いでイミド化剤によって化学イミド化する方法や、１４０～２７０℃程度の高温で加熱して熱イミド化する２工程からなる方法、或いは始めから１４０～２７０℃の高温で、０．１～５０時間重合・イミド化反応を行わせる１工程からなる方法を例示できる。
　これらの反応で用いる溶媒は、これに限定されないが、Ｎ－メチル－２－ピロリドン、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ，Ｎ－ジエチルアセトアミド、γ－ブチルラクトン、Ｎ－メチルカプロラクタム等の有機極性溶媒を好適に使用できる。 [Addition reaction type polyimide resin]
In the present invention, it is an important feature that an addition reaction type polyimide resin is used as a polyimide resin to be a matrix of a composition constituting a fiber reinforced polyimide resin molded body.
The addition reaction type polyimide resin used in the present invention is composed of an aromatic polyimide oligomer having an addition reaction group at the terminal, and those prepared by a conventionally known production method can be used. For example, an aromatic tetracarboxylic dianhydride, an aromatic diamine, and a compound having an anhydride group or an amino group together with an addition reactive group in the molecule, the total of the equivalent of each acid group and the total of each amino group are approximately It can be easily obtained by using it so that it may become equal amount, and making it react in a solvent suitably. As a method for the reaction, a method of polymerizing at a temperature of 100 ° C. or lower, preferably 80 ° C. or lower for 0.1 to 50 hours to form an oligomer having an amic acid bond, and then chemically imidizing with an imidizing agent, , A method comprising two steps of heat imidization by heating at a high temperature of about 140 to 270 ° C., or one step of performing a polymerization / imidization reaction at a high temperature of 140 to 270 ° C. for 0.1 to 50 hours from the beginning. Can be exemplified.
The solvent used in these reactions is not limited to this, but N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, γ-butyllactone, N- An organic polar solvent such as methylcaprolactam can be preferably used.
　本発明において、芳香族イミドオリゴマーの末端の付加反応基は、樹脂成形体を製造する際に、加熱によって硬化反応（付加重合反応）を行う基であれば特に限定されないが、好適に硬化反応を行うことができること、及び得られた硬化物の耐熱性が良好であることを考慮すると、好ましくはフェニルエチニル基、アセチレン基、ナジック酸基、及びマレイミド基からなる群から選ばれるいずれかの反応基であることが好ましく、特にフェニルエチニル基は、硬化反応によるガス成分の発生がなく、しかも得られた樹脂成形体の耐熱性に優れていると共に機械的な強度にも優れていることから好適である。
　これらの付加反応基は、分子内に付加反応基と共に無水物基又はアミノ基を有する化合物が、芳香族イミドオリゴマーの末端のアミノ基又は酸無水物基と、好適にはイミド環を形成する反応によって、芳香族イミドオリゴマーの末端に導入される。
　分子内に付加反応基と共に無水物基又はアミノ基を有する化合物は、例えば４－（２－フェニルエチニル）無水フタル酸、４－（２－フェニルエチニル）アニリン、４－エチニル－無水フタル酸、４－エチニルアニリン、ナジック酸無水物、マレイン酸無水物等を好適に使用することができる。 In the present invention, the terminal addition reaction group of the aromatic imide oligomer is not particularly limited as long as it is a group that undergoes a curing reaction (addition polymerization reaction) by heating when producing a resin molded body, but preferably performs a curing reaction. In consideration of what can be performed and the heat resistance of the obtained cured product is good, any reactive group selected from the group consisting of a phenylethynyl group, an acetylene group, a nadic acid group, and a maleimide group is preferable. In particular, the phenylethynyl group is suitable because it does not generate a gas component due to the curing reaction, and is excellent in the heat resistance and mechanical strength of the obtained resin molded body. is there.
These addition-reactive groups are a reaction in which a compound having an anhydride group or amino group together with an addition reactive group in the molecule forms an imide ring, preferably with an amino group or acid anhydride group at the terminal of an aromatic imide oligomer. Is introduced at the end of the aromatic imide oligomer.
Compounds having an anhydride group or amino group in the molecule together with an anhydride group or an amino group include, for example, 4- (2-phenylethynyl) phthalic anhydride, 4- (2-phenylethynyl) aniline, 4-ethynyl-phthalic anhydride, 4 -Ethynylaniline, nadic acid anhydride, maleic acid anhydride and the like can be preferably used.
　末端に付加反応基を有する芳香族イミドオリゴマーを形成するテトラカルボン酸成分としては、２，３，３’，４’－ビフェニルテトラカルボン酸二無水物、２，２’，３，３’－ビフェニルテトラカルボン酸二無水物、３，３’，４，４’－ビフェニルテトラカルボン酸二無水物、及び３，３’，４，４’－ベンゾフェノンテトラカルボン酸二無水物からなる群から選ばれる少なくとも一つのテトラカルボン酸二無水物を例示することができ、特に、２，３，３’，４’－ビフェニルテトラカルボン酸二無水物を好適に使用することができる。 Examples of the tetracarboxylic acid component that forms an aromatic imide oligomer having an addition reactive group at the terminal include 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyl At least selected from the group consisting of tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, and 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride One tetracarboxylic dianhydride can be exemplified, and in particular, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride can be preferably used.
　末端に付加反応基を有する芳香族イミドオリゴマーを形成するジアミン成分としては、これに限定されないが、１，４－ジアミノベンゼン、１，３－ジアミノベンゼン、１，２－ジアミノベンゼン、２，６－ジエチル－１，３－ジアミノベンゼン、４，６－ジエチル－２－メチル－１,３-ジアミノベンゼン、３，５－ジエチルトルエン－２，４－ジアミン、３，５－ジエチルトルエン－２，６－ジアミン等のベンゼン環を１個有するジアミン、４，４’－ジアミノジフェニルエーテル、３，４’－ジアミノジフェニルエーテル、３，３’－ジアミノジフェニルエーテル、３，３’－ジアミノベンゾフェノン、４，４’－ジアミノベンゾフェノン、４，４’－ジアミノジフェニルメタン、３，３’－ジアミノジフェニルメタン、ビス(２，６－ジエチル－４－アミノフェノキシ)メタン、ビス(２－エチル－６－メチル－４－アミノフェニル)メタン、４，４’－メチレン－ビス(２，６－ジエチルアニリン)、４，４’－メチレン－ビス(２－エチル，６－メチルアニリン)、２，２―ビス(３－アミノフェニル)プロパン、２，２―ビス(４－アミノフェニル)プロパン、ベンジジン、２，２’－ビス（トリフルオロメチル）ベンジジン、３，３’－ジメチルベンジジン、２，２－ビス（４－アミノフェニル）プロパン、２，２－ビス（３－アミノフェニル）プロパン等のベンゼン環を２個有するジアミン、１，３－ビス（４－アミノフェノキシ）ベンゼン、１，３－ビス（３－アミノフェノキシ）ベンゼン，１，４－ビス（４－アミノフェノキシ）ベンゼン、１，４－ビス（３－アミノフェノキシ）ベンゼン等のベンゼン環を３個有するジアミン２，２－ビス［４－［４－アミノフェノキシ］フェニル］プロパン、２，２－ビス［４－［４－アミノフェノキシ］フェニル］ヘキサフルオロプロパン等のベンゼン環を４個有するジアミン等を単独、或いは複数種混合して使用することができる。 The diamine component that forms the aromatic imide oligomer having an addition reactive group at the terminal is not limited to this, but 1,4-diaminobenzene, 1,3-diaminobenzene, 1,2-diaminobenzene, 2,6- Diethyl-1,3-diaminobenzene, 4,6-diethyl-2-methyl-1,3-diaminobenzene, 3,5-diethyltoluene-2,4-diamine, 3,5-diethyltoluene-2,6- Diamine having one benzene ring such as diamine, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, 3,3′-diaminobenzophenone, 4,4′-diaminobenzophenone 4,4′-diaminodiphenylmethane, 3,3′-diaminodiphenylmethane, bis (2,6- Ethyl-4-aminophenoxy) methane, bis (2-ethyl-6-methyl-4-aminophenyl) methane, 4,4′-methylene-bis (2,6-diethylaniline), 4,4′-methylene- Bis (2-ethyl, 6-methylaniline), 2,2-bis (3-aminophenyl) propane, 2,2-bis (4-aminophenyl) propane, benzidine, 2,2'-bis (trifluoromethyl) ) Diamines having two benzene rings such as benzidine, 3,3′-dimethylbenzidine, 2,2-bis (4-aminophenyl) propane, 2,2-bis (3-aminophenyl) propane, 1,3- Bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) Ii) Diamine having three benzene rings such as benzene 2,2-bis [4- [4-aminophenoxy] phenyl] propane, 2,2-bis [4- [4-aminophenoxy] phenyl] hexafluoropropane, etc. These diamines having four benzene rings can be used alone or in combination.
　これらの中でも、１，３－ジアミノベンゼン、１，３－ビス（４－アミノフェノキシ）ベンゼン、３，４’－ジアミノジフェニルエーテル、４，４’－ジアミノジフェニルエーテル、及び２，２’－ビス（トリフルオロメチル）ベンジジンからなる群から選ばれる少なくとも二つの芳香族ジアミンによって構成された混合ジアミンを用いることが好適であり、特に、１，３－ジアミノベンゼンと１，３－ビス（４－アミノフェノキシ）ベンゼンとの組み合せからなる混合ジアミン、３，４’－ジアミノジフェニルエーテルと４，４’－ジアミノジフェニルエーテルとの組み合せからなる混合ジアミン、３，４’－ジアミノジフェニルエーテルと１，３－ビス（４－アミノフェノキシ）ベンゼンとの組み合せからなる混合ジアミン、４，４’－ジアミノジフェニルエーテルと１，３－ビス（４－アミノフェノキシ）ベンゼンとの組み合せからなる混合ジアミン、及び２，２’－ビス（トリフルオロメチル）ベンジジンと１，３－ビス（４－アミノフェノキシ）ベンゼンとの組み合せからなる混合ジアミンを使用することが、耐熱性と成形性の点から好適である。 Among these, 1,3-diaminobenzene, 1,3-bis (4-aminophenoxy) benzene, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, and 2,2'-bis (trifluoro) It is preferable to use a mixed diamine composed of at least two aromatic diamines selected from the group consisting of methyl) benzidine, particularly 1,3-diaminobenzene and 1,3-bis (4-aminophenoxy) benzene. Mixed diamine consisting of a combination of 2,4'-diaminodiphenyl ether and 4,4'-diaminodiphenyl ether, diamine, 3,4'-diaminodiphenyl ether and 1,3-bis (4-aminophenoxy) Mixed diamine consisting of a combination with benzene, 4,4 ' A mixed diamine comprising a combination of diaminodiphenyl ether and 1,3-bis (4-aminophenoxy) benzene, and 2,2′-bis (trifluoromethyl) benzidine and 1,3-bis (4-aminophenoxy) benzene From the viewpoint of heat resistance and moldability, it is preferable to use a mixed diamine comprising a combination of the above.
　本発明で用いる末端に付加反応基を有する芳香族イミドオリゴマーは、イミドオリゴマーの繰返し単位の繰返し数が、０より大きく２０以下、特に１～５であることが好適であり、ＧＰＣによるスチレン換算の数平均分子量が、１００００以下、特に３０００以下であることが好適である。繰返し単位の繰返し数が上記範囲にあることにより、溶融粘度が適切な範囲に調整されて、機能性繊維を均一に混合することが可能になる。また高温で成形する必要がなく、成形性に優れていると共に、耐熱性、機械的強度に優れた樹脂成形体を提供することが可能になる。
　繰返し単位の繰返し数の調整は、芳香族テトラカルボン酸二無水物、芳香族ジアミン、及び分子内に付加反応基と共に無水物基又はアミノ基を有する化合物の割合を変えることにより行うことができ、分子内に付加反応基と共に無水物基又はアミノ基を有する化合物の割合を高くすることにより、低分子量化して繰返し単位の繰返し数は小さくなり、この化合物の割合を小さくすると、高分子量化して繰返し単位の繰返し数は大きくなる。 In the aromatic imide oligomer having an addition reactive group at the terminal used in the present invention, the number of repeating units of the imide oligomer is preferably more than 0 and 20 or less, particularly 1 to 5, and is preferably in terms of styrene by GPC. The number average molecular weight is preferably 10,000 or less, particularly 3000 or less. When the number of repeating units is in the above range, the melt viscosity is adjusted to an appropriate range, and the functional fibers can be mixed uniformly. Further, it is not necessary to mold at a high temperature, and it becomes possible to provide a resin molded body having excellent moldability and excellent heat resistance and mechanical strength.
Adjustment of the number of repeating units can be performed by changing the ratio of aromatic tetracarboxylic dianhydride, aromatic diamine, and compound having an anhydride group or amino group together with an addition reactive group in the molecule, By increasing the proportion of the compound having an anhydride group or amino group in the molecule and an anhydride group or amino group, the number of repeating units is reduced by lowering the molecular weight. The number of unit repetitions increases.
　付加反応型ポリイミド樹脂には、目的とする樹脂成形体の用途に応じて、難燃剤、着色剤、滑剤、熱安定剤、光安定剤、紫外線吸収剤、充填剤等の樹脂添加剤を公知の処方に従って配合することができる。 For addition reaction type polyimide resins, known resin additives such as flame retardants, colorants, lubricants, heat stabilizers, light stabilizers, ultraviolet absorbers, fillers, etc., are known depending on the intended use of the resin molding. It can be blended according to the prescription.
[機能性繊維]
　本発明において、上述した付加反応型ポリイミド樹脂中に分散させる機能性繊維としては、従来公知の物を使用することができ、炭素繊維、アラミド繊維、ガラス繊維、金属繊維等、従来公知の機能性繊維を使用することができるが、特に炭素繊維を好適に用いることができる。
　中でも、平均繊維長が５０～６０００μｍ及び平均繊維径が５～２０μｍの範囲にある炭素繊維を好適に使用することができる。上記範囲よりも平均繊維長が短い場合には、炭素繊維の強化材としての効果を充分に得ることができず、その一方上記範囲よりも長いとポリイミド樹脂中での分散性に劣るようになる。また上記範囲よりも平均繊維径が細い場合には、取扱い性に劣ると共に高価であり、一方上記範囲よりも平均繊維径が太い場合には機能性繊維の沈降速度が増大して、機能性繊維が偏在しやすくなるおそれがあると共に、繊維の強度が低下する傾向があり、強化材としての効果を充分に得られないおそれがある。 [Functional fibers]
In the present invention, as the functional fiber to be dispersed in the above-described addition reaction type polyimide resin, conventionally known materials can be used, and conventionally known functionalities such as carbon fiber, aramid fiber, glass fiber, metal fiber, etc. Although fibers can be used, carbon fibers can be particularly preferably used.
Of these, carbon fibers having an average fiber length of 50 to 6000 μm and an average fiber diameter of 5 to 20 μm can be preferably used. When the average fiber length is shorter than the above range, the effect of carbon fiber as a reinforcing material cannot be sufficiently obtained. On the other hand, when the average fiber length is longer than the above range, the dispersibility in the polyimide resin becomes poor. . Further, when the average fiber diameter is thinner than the above range, the handling property is inferior and expensive, while when the average fiber diameter is thicker than the above range, the settling rate of the functional fiber is increased and the functional fiber is increased. May tend to be unevenly distributed, and the strength of the fiber tends to decrease, and the effect as a reinforcing material may not be sufficiently obtained.
　機能性繊維の含有量は、樹脂成形体の摺動性能及び成形時の反りの発生に重大な影響を有しており、本発明においては、機能性繊維は、付加反応型ポリイミド１００重量部に対して５～２００重量部、特に１０～１５０重量部の量で含有されていることが、優れた摺動性能を有すると共に、反りがなく優れた形状安定性を有する成形体を得る上で好適である。上記範囲よりも機能性繊維の量が少ないと、限界ＰＶ値が上記値未満になり摺動性が低下するおそれがある。また樹脂成形体の反りの発生が増大するおそれもある。一方上記範囲よりも機能性繊維の量が多いと、上記範囲にある場合に比して限界ＰＶ値が低下するおそれがある。また過度の増粘が生じ、賦型できないおそれがある。 The content of the functional fiber has a significant influence on the sliding performance of the resin molded body and the occurrence of warpage during molding. In the present invention, the functional fiber is added to 100 parts by weight of the addition reaction type polyimide. Containing 5 to 200 parts by weight, particularly 10 to 150 parts by weight, is suitable for obtaining a molded article having excellent sliding performance and excellent shape stability without warping. It is. When the amount of the functional fiber is less than the above range, the limit PV value is less than the above value, and the slidability may be lowered. Moreover, there is a possibility that the occurrence of warping of the resin molded body increases. On the other hand, when the amount of the functional fiber is larger than the above range, the limit PV value may be lowered as compared with the case where the amount is within the above range. In addition, excessive thickening may occur and molding may not be possible.
　本発明においては、上記機能性繊維と共に、カーボンブラック等の微細炭素系材料、アルミ粉、銅粉等の金属粉等の無機材料の少なくとも一種を配合することもできる。
　上記無機材料は、付加反応型ポリイミド１００重量部に対して５～４０重量部の量で含有されていることが好適である。 In the present invention, together with the functional fibers, at least one of inorganic materials such as fine carbon-based materials such as carbon black, metal powders such as aluminum powder and copper powder can be blended.
The inorganic material is preferably contained in an amount of 5 to 40 parts by weight with respect to 100 parts by weight of the addition reaction type polyimide.
［増粘剤］
　本発明においては、上記機能性繊維と共に増粘剤を付加反応型ポリイミド１００重量部に対して５～４０重量部の量で用いることにより、付加反応型ポリアミド樹脂のプレポリマーの粘度を増粘工程を経ることなく増大させることが可能になり、これにより機能性繊維は沈降することなく、プレポリマー中に均一に分散した状態を維持できる。
　増粘剤としては、グラファイト、二硫化モリブデン、ＰＴＦＥ（四フッ化エチレン樹脂）、酸化マグネシウム、水酸化マグネシウム、水酸化カルシウム等を使用することができるが、中でもグラファイト、二硫化モリブデン、ＰＴＦＥは、摺動性能を更に向上させることもできるので特に好適である。
　増粘剤は、上述したとおり、付加反応型ポリイミド１００重量部に対して５～４０重量部の量で含有されていることが好適である。上記範囲よりも増粘剤の量が少ないと、プレポリマーの粘度が十分に増加せず、機能性繊維の沈降を充分に抑制することができず、機能性繊維が均一分散している反り変形のない樹脂成形体を成形することができない。また上記範囲よりも増粘剤の量が多くなると摩擦係数の増大や耐摩耗性の低下等、摺動性能を損なうおそれがある。 [Thickener]
In the present invention, the viscosity of the prepolymer of the addition reaction type polyamide resin is increased by using the thickener together with the functional fiber in an amount of 5 to 40 parts by weight with respect to 100 parts by weight of the addition reaction type polyimide. Thus, the functional fibers can be maintained uniformly dispersed in the prepolymer without settling.
As the thickener, graphite, molybdenum disulfide, PTFE (tetrafluoroethylene resin), magnesium oxide, magnesium hydroxide, calcium hydroxide, and the like can be used. Among them, graphite, molybdenum disulfide, PTFE, The sliding performance can be further improved, which is particularly preferable.
As described above, the thickener is preferably contained in an amount of 5 to 40 parts by weight based on 100 parts by weight of the addition reaction type polyimide. If the amount of the thickener is less than the above range, the viscosity of the prepolymer does not increase sufficiently, the settling of the functional fibers cannot be sufficiently suppressed, and the warp deformation in which the functional fibers are uniformly dispersed It is not possible to mold a resin molded body without any. Further, if the amount of the thickener is larger than the above range, the sliding performance may be impaired, such as an increase in coefficient of friction and a decrease in wear resistance.
（樹脂成形体の第一の製造方法）
　本発明の樹脂成形体の第一の製造方法は、少なくとも、付加反応型ポリイミド樹脂のプレポリマー（イミドオリゴマー）と機能性繊維を付加反応型ポリイミド樹脂の融点以上、熱硬化開始温度以下の温度で混練する分散混練工程（Ａ）、分散混練工程を経た混合物を反応型ポリイミド樹脂の熱硬化開始温度以上の温度条件下で加圧賦形する賦形工程（Ｃ）、から成り、必要により、前記分散混練工程（Ａ）と賦形工程（Ｃ）の間に、分散混練工程により得られた混練物を反応型ポリイミド樹脂の熱硬化開始温度以上の温度で一定時間保持することにより混練物の粘度を必要に応じて上昇させ適正範囲に混練物の粘度を調整する増粘工程（Ｂ）を有することを特徴とする。
　前述したとおり、本発明の樹脂成形体の成形に用いる付加反応型ポリイミド樹脂は、架橋硬化前のプレポリマーの状態では低粘度であることから、機能性繊維を含有させると沈降してしまい、その結果、機能性繊維が遍在し、成形体に反りが発生する。本発明の第一の製造方法においては、上記分散混練工程（Ａ）後に、上記増粘工程（Ｂ）によりプレポリマーの粘度を増大させることにより機能性繊維の沈降を防止して、その状態を維持したまま賦形工程（Ｃ）で賦形されることから、機能性繊維が均一に分散し、加熱硬化の際に均等に収縮して反りのない成形体を成形することが可能になる。 (First manufacturing method of resin molding)
The first manufacturing method of the resin molded body of the present invention is at least a prepolymer (imide oligomer) of an addition reaction type polyimide resin and a functional fiber at a temperature not lower than the melting point of the addition reaction type polyimide resin and not higher than the thermosetting start temperature. Dispersing and kneading step (A) for kneading, and shaping step (C) for press-molding the mixture that has undergone the dispersion kneading step under a temperature condition equal to or higher than the thermal curing start temperature of the reactive polyimide resin. Between the dispersion kneading step (A) and the shaping step (C), the viscosity of the kneaded product is maintained by holding the kneaded product obtained by the dispersion kneading step at a temperature equal to or higher than the thermal curing start temperature of the reactive polyimide resin for a certain period of time. It is characterized by having a thickening step (B) in which the viscosity of the kneaded product is adjusted to an appropriate range by raising the viscosity as necessary.
As described above, the addition reaction type polyimide resin used for molding the resin molded body of the present invention has a low viscosity in the state of the prepolymer before cross-linking and curing, and when functional fibers are contained, it settles. As a result, functional fibers are ubiquitous and warping occurs in the molded body. In the first production method of the present invention, after the dispersion kneading step (A), the viscosity of the prepolymer is increased by the thickening step (B) to prevent sedimentation of the functional fiber, and the state thereof is changed. Since it is shaped in the shaping step (C) while being maintained, the functional fibers are uniformly dispersed, and it becomes possible to mold a molded product without warping by shrinking evenly during heat curing.
[分散混練工程]
　付加反応型ポリイミド樹脂のプレポリマー（イミドオリゴマー）と機能性繊維を付加反応型ポリイミド樹脂の融点以上の温度で加熱しプレポリマーを溶融しながら混練することにより、プレポリマーと機能性繊維を混合する。この際、前述したとおり、付加反応型ポリイミド１００重量部に対して機能性繊維を５～２００重量部、特に１０～１５０重量部の量で用いる。また上述した無機材料を上述した量配合することもできる。また特に必要はないが、上述した増粘剤を上述した量で配合することもできる。
　プレポリマー及び機能性繊維の混練は、ヘンシェルミキサー、タンブラーミキサー、リボンブレンダ―等の従来公知の混合機を用いることもできるが、機能性繊維の破断を抑制すると共に均一に分散させることが重要であることから、バッチ式の加圧ニーダー（混練機）を用いることが特に好適である。 [Dispersion kneading process]
The prepolymer and the functional fiber are mixed by heating the prepolymer (imide oligomer) of the addition reaction type polyimide resin and the functional fiber at a temperature equal to or higher than the melting point of the addition reaction type polyimide resin and kneading while melting the prepolymer. . At this time, as described above, the functional fiber is used in an amount of 5 to 200 parts by weight, particularly 10 to 150 parts by weight, based on 100 parts by weight of the addition reaction type polyimide. Further, the above-mentioned inorganic materials can be blended in the above-mentioned amounts. Although not particularly necessary, the above-mentioned thickener can be blended in the above-mentioned amount.
For the kneading of the prepolymer and the functional fiber, a conventionally known mixer such as a Henschel mixer, a tumbler mixer, or a ribbon blender can be used. However, it is important to suppress the breakage of the functional fiber and to disperse it uniformly. Therefore, it is particularly preferable to use a batch type pressure kneader (kneader).
　本発明においては、分散混練工程を経たプレポリマーと機能性繊維の混合物を冷却固化した後、所定の大きさの塊状にしておくことが望ましい。これにより、機能性繊維がプレポリマーに分散した混合物を経時保管することが可能になり、取扱い性も向上する。 In the present invention, it is desirable to cool and solidify the mixture of prepolymer and functional fiber that has undergone the dispersion-kneading step, and then form a lump of a predetermined size. Thereby, it becomes possible to store the mixture in which the functional fibers are dispersed in the prepolymer with the lapse of time, and the handleability is also improved.
［増粘工程］
　次いで、溶融混練されたプレポリマーと機能性繊維の混合物の３００～３２０℃の温度条件下における溶融粘度が１０以下である場合、その混合物に用いるポリイミド樹脂の熱硬化開始温度近傍３１０±１０℃の温度で３０～６０分間保持することにより、３００～３２０℃の温度条件下における溶融粘度を１０～５０００Ｐａ・ｓの範囲に調整する。
　すなわち、プレポリマーと機能性繊維の混合物を、電気炉等を用いて３１０±１０℃の温度で３０～６０分間保持することにより、プレポリマーが徐々に架橋し始めることから粘度は上昇する。更に前記分散混練工程によりプレポリマー中に含浸された機能性繊維はこの粘度上昇によりプレポリマー中で沈降することなく分散状態を維持できる。また上記範囲の加熱温度及び保持時間にすることで、プレポリマーを完全に架橋硬化させることなく、粘度のみを上記範囲に上昇させることが可能になる。従って、増粘工程は、プレポリマーの熱硬化開始温度以上、且つ、完全に架橋硬化する温度未満にて行う。
　尚、付加反応型ポリイミド樹脂においては、反応開始温度は付加反応基に依存し、本発明において付加反応基として好適なフェニルエチニル基を有するポリイミド樹脂においては、熱硬化開始温度近傍である３１０±１０℃の温度で３０～６０分間加熱することが望ましい。 [Thickening process]
Next, when the melt viscosity of the mixture of the melt-kneaded prepolymer and the functional fiber under a temperature condition of 300 to 320 ° C. is 10 or less, the temperature of the polyimide resin used in the mixture is about 310 ± 10 ° C. near the thermosetting start temperature. By maintaining the temperature at 30 to 60 minutes, the melt viscosity under the temperature condition of 300 to 320 ° C. is adjusted to the range of 10 to 5000 Pa · s.
That is, when the mixture of the prepolymer and the functional fiber is held at a temperature of 310 ± 10 ° C. for 30 to 60 minutes using an electric furnace or the like, the prepolymer gradually starts to crosslink, so that the viscosity increases. Furthermore, the functional fiber impregnated in the prepolymer by the dispersion kneading step can maintain a dispersed state without settling in the prepolymer due to this viscosity increase. Moreover, it becomes possible to raise only a viscosity to the said range, without making a prepolymer completely bridge | crosslink and harden | cure by setting it as the heating temperature and holding time of the said range. Therefore, the thickening step is performed at a temperature higher than the heat curing start temperature of the prepolymer and lower than a temperature at which it is completely crosslinked and cured.
In addition, in the addition reaction type polyimide resin, the reaction start temperature depends on the addition reaction group, and in the polyimide resin having a phenylethynyl group suitable as the addition reaction group in the present invention, 310 ± 10 which is close to the thermosetting start temperature. It is desirable to heat at a temperature of 30 ° C. for 30 to 60 minutes.
［賦形工程］
　増粘工程を経て溶融粘度が上記範囲に調整されたプレポリマー及び機能性繊維の混合物は、用いるポリイミド樹脂の熱硬化開始温度以上の温度条件下で賦形し、所望の形状の樹脂成形体として成形される。
　賦形工程を行う場合には、溶融状態にある上記の粘度範囲にあるポリイミドプレポリマーと機能性繊維の混合物を、成形型に導入して熱硬化開始温度以上の温度で加熱加圧することにより硬化させて樹脂成形体を成形する。
　尚、賦形は、成形型に導入された混合物を加圧圧縮して成形する圧縮成形やトランスファー成形によることが好適であるが、射出成形や押出成形によっても成形することができる。 [Shaping process]
The mixture of the prepolymer and the functional fiber whose melt viscosity is adjusted to the above range through the thickening step is shaped under a temperature condition equal to or higher than the thermosetting start temperature of the polyimide resin to be used as a resin molded body having a desired shape. Molded.
When performing the shaping step, the mixture is cured by introducing a mixture of the polyimide prepolymer and functional fibers in the above-mentioned viscosity range in the molten state into a mold and heating and pressing at a temperature equal to or higher than the thermosetting start temperature. To form a resin molded body.
The shaping is preferably performed by compression molding or transfer molding in which the mixture introduced into the molding die is compressed and compressed, but can also be molded by injection molding or extrusion molding.
（樹脂成形体の第二の製造方法）
　本発明の樹脂成形体の第二の製造方法は、付加反応型ポリイミド樹脂のプレポリマー（イミドオリゴマー）１００重量部に対して５～２００重量部の機能性繊維及び５～４０重量部の増粘剤を、付加反応型ポリイミド樹脂の融点以上、熱硬化開始温度以下の温度で混練する分散混練工程、及び前記分散混練工程を経た混合物を反応型ポリイミド樹脂の熱硬化開始温度以上の温度条件下で加圧賦形する賦形工程、とから成ることを特徴とする。
　前述したとおり、本発明の樹脂成形体の成形に用いる付加反応型ポリイミド樹脂は、架橋硬化前のプレポリマーの状態では低粘度であることから、機能性繊維を含有させると沈降してしまい、その結果、機能性繊維が遍在し、成形体に反りが発生する。本発明の第二の製造方法においては、機能性繊維と共に所定量の増粘剤をプレポリマーに配合することにより、増粘工程を経ることなく、プレポリマーの粘度を増大させることが可能になり、その結果、プレポリマー中で機能性繊維が沈降することなく分散し、機能性繊維が分散した状態を維持したまま賦形工程で賦形されることから、加熱硬化の際に均等に収縮して反りのない成形体を成形することが可能になる。 (Second production method of resin molded body)
The second production method of the resin molded body of the present invention is such that 5 to 200 parts by weight of functional fiber and 5 to 40 parts by weight of thickening agent are added to 100 parts by weight of the prepolymer (imide oligomer) of the addition reaction type polyimide resin. A dispersion kneading step in which the agent is kneaded at a temperature not lower than the melting point of the addition reaction type polyimide resin and not higher than the thermosetting start temperature, and the mixture having undergone the dispersion kneading step is subjected to a temperature condition not lower than the thermosetting start temperature of the reaction type polyimide resin. It is characterized by comprising a shaping step for pressure shaping.
As described above, the addition reaction type polyimide resin used for molding the resin molded body of the present invention has a low viscosity in the state of the prepolymer before cross-linking and curing, and when functional fibers are contained, it settles. As a result, functional fibers are ubiquitous and warping occurs in the molded body. In the second production method of the present invention, it is possible to increase the viscosity of the prepolymer without passing through the thickening step by adding a predetermined amount of thickener together with the functional fiber to the prepolymer. As a result, the functional fibers are dispersed without precipitating in the prepolymer, and the functional fibers are formed in the shaping process while maintaining the dispersed state. Thus, it becomes possible to mold a molded body without warping.
[分散混練工程]
　付加反応型ポリイミド樹脂のプレポリマー（イミドオリゴマー）と機能性繊維及び増粘剤を、付加反応型ポリイミド樹脂の融点以上の温度で加熱しプレポリマーを溶融しながら混練することにより、プレポリマーと機能性繊維を混合する。この際、前述したとおり、付加反応型ポリイミド１００重量部に対して機能性繊維を５～２００重量部、特に１０～１５０重量部、増粘剤を５～４０重量部の量で用いる。
　プレポリマー及び機能性繊維の混練は、前述した第一の製造方法と同様に行うことができる。
　この態様において、分散混練工程の温度は、プレポリマーの融点以上、且つ架橋硬化する温度以下、特に好ましくは、分散混練工程を経た混合物が、３００～３２０℃の温度条件下での溶融粘度が１０～５０００Ｐａ・ｓの範囲にあることが好ましい。この粘度上昇と機能性繊維にプレポリマーが浸透することとが相俟って、機能性繊維は沈降することなく、プレポリマー中に分散した状態を維持する。
　分散混練工程を経たプレポリマーと機能性繊維及び増粘剤の混合物は、冷却固化した後、所定の大きさの塊状にしておくことが望ましい。これにより、機能性繊維がプレポリマーに分散した混合物を経時保管することが可能になり、取扱い性も向上する。 [Dispersion kneading process]
Prepolymer (imide oligomer) of addition reaction type polyimide resin, functional fiber, and thickener are heated at a temperature equal to or higher than the melting point of addition reaction type polyimide resin and kneaded while melting the prepolymer. Mix sex fibers. At this time, as described above, the functional fiber is used in an amount of 5 to 200 parts by weight, particularly 10 to 150 parts by weight, and the thickener 5 to 40 parts by weight with respect to 100 parts by weight of the addition reaction type polyimide.
The kneading of the prepolymer and the functional fiber can be performed in the same manner as in the first production method described above.
In this embodiment, the temperature of the dispersion kneading step is equal to or higher than the melting point of the prepolymer and equal to or lower than the crosslinking curing temperature, and particularly preferably, the mixture that has undergone the dispersion kneading step has a melt viscosity of 10 at a temperature of 300 to 320 ° C. It is preferably in the range of ˜5000 Pa · s. The increase in viscosity and the penetration of the prepolymer into the functional fiber are combined, and the functional fiber does not settle and maintains a state dispersed in the prepolymer.
It is desirable that the mixture of the prepolymer, the functional fiber, and the thickener that has undergone the dispersion kneading step is cooled and solidified and then formed into a lump of a predetermined size. Thereby, it becomes possible to store the mixture in which the functional fibers are dispersed in the prepolymer with the lapse of time, and the handleability is also improved.
［賦形工程］
　分散混練工程を経て溶融粘度が上記範囲に調整されたプレポリマー、機能性繊維及び増粘剤の混合物の賦形は、前述した第一の製造方法における賦形と同様に行うことができる。 [Shaping process]
The shaping of the mixture of the prepolymer, the functional fiber and the thickener whose melt viscosity is adjusted to the above range through the dispersion kneading step can be performed in the same manner as the shaping in the first production method described above.
（限界ＰＶ値の測定）
　ＪＩＳ　Ｋ　７２１８（プラスチックの滑り摩耗試験方法）に適合したスラスト型摩耗試験機を用い、図１に示すようなリングオンディスク式にて速度一定の条件下で５分又は１０分おきに面圧を上昇させ、摩擦力が急激に上昇する或いは著しい変形と摩耗粉が発生したところを限界とし、限界時の１つ前の面圧（Ｐ）と速度（Ｖ）の積を限界ＰＶ値とした。
　限界ＰＶ値測定条件
　試験速度；０．５ｍ／ｓ、初期面圧；０．５ＭＰａ
　面圧ステップ ０．５ＭＰａ／１０ｍｉｎ（～１０ＭＰａ）
　　　　　　１ＭＰａ／１０ｍｉｎ（１０ＭＰａ～）
　相手材　：Ｓ４５Ｃリング　表面粗さＲａ０．８μｍ
　　　　　　外径２５．６ｍｍ、内径２０ｍｍ（接触面積２ｃｍ２）
　試験環境：２３±２℃、５０％±５％ＲＨ
　試験機：エー・アンド・デイ社製　摩擦摩耗試験機　ＥＭＦ－III－Ｆ (Measurement of limit PV value)
Using a thrust type wear tester conforming to JIS K 7218 (plastic sliding wear test method), the surface pressure is applied every 5 or 10 minutes under a constant speed condition in a ring-on-disk type as shown in FIG. The limit was defined as a point where the frictional force increased abruptly or significant deformation and abrasion powder were generated, and the product of the previous surface pressure (P) and speed (V) at the limit was defined as the limit PV value.
Critical PV value measurement conditions Test speed: 0.5 m / s, initial surface pressure: 0.5 MPa
Surface pressure step 0.5MPa / 10min (~ 10MPa)
1MPa / 10min (10MPa ~)
Opposite material: S45C ring surface roughness Ra 0.8μm
Outer diameter 25.6 mm, inner diameter 20 mm (contact area 2 cm 2 )
Test environment: 23 ± 2 ° C., 50% ± 5% RH
Testing machine: A & D Friction and Wear Testing Machine EMF-III-F
（繊維の分散）
　成形体の断面を観察し、繊維の偏在の有無を目視または走査電子顕微鏡（日立ハイテクテクノロジー社製Ｓ－３４００Ｎ）による観察にて確認した。繊維が分散しているものを○、繊維の沈降がみられるものを×とした。 (Dispersion of fiber)
The cross section of the molded body was observed, and the presence or absence of uneven distribution of fibers was confirmed by visual observation or observation with a scanning electron microscope (S-3400N manufactured by Hitachi High-Technology Corporation). A sample in which fibers were dispersed was marked with ◯, and a sample in which fibers settled was marked with ×.
（反り量の測定）
　図２に示す試験片反り量ｔ（ｍｍ）、製品直径寸法Ｄ（ｍｍ）を測定し、反り／直径比を以下の式（１）により算出した。
　反り／直径比（％）＝ｔ／Ｄ×１００
　ｔ：試験片反り量（ｍｍ）、Ｄ：製品直径（ｍｍ）
　なお反り／直径比の良否判定は１．５％未満を○、１．５％以上を×とした。 (Measurement of warpage)
The specimen warpage amount t (mm) and the product diameter dimension D (mm) shown in FIG. 2 were measured, and the warpage / diameter ratio was calculated by the following equation (1).
Warpage / Diameter ratio (%) = t / D × 100
t: Test piece warpage (mm), D: Product diameter (mm)
In addition, the quality determination of the warp / diameter ratio was evaluated as ○ when less than 1.5% and × when 1.5% or more.
（溶融粘度の測定）
　３１０℃における溶融粘度をレオメータ（ＴＡ　ｉｎｓｔｒｕｍｅｎｔ社製ＡＲＥＳ）により測定した。測定モードを動的周波数分散として、角周波数を０．１～５００ｒａｄ／ｓとし、０．１ｒａｄ／ｓの条件における溶融粘度を測定値とした。 (Measurement of melt viscosity)
The melt viscosity at 310 ° C. was measured with a rheometer (ARES manufactured by TA instrument). The measurement mode was dynamic frequency dispersion, the angular frequency was 0.1 to 500 rad / s, and the melt viscosity under the condition of 0.1 rad / s was taken as the measured value.
（実施例１）
　付加重合型ポリイミド（宇部興産社製ＰＥＴＩ－３３０）１００重量部に対して、平均単繊維長さ２００μｍのピッチ系炭素繊維（三菱樹脂社製Ｋ２２３ＨＭ）１１．１重量部を配合し、ニーダーにより大気圧下２８０℃、３０分で溶融混練した。その後、室温まで冷却された混合物（バルクモールディングコンパウンド、以下ＢＭＣ）を得た。得られたＢＭＣを扱いが容易なサイズに割ってから３１０℃、３０分電気炉内に保持し、急冷、再度粉砕した樹脂混合体（増粘ＢＭＣ）を圧縮成形機用金型内で、２８０℃～３２０℃で一定時間保持することで溶融および均熱した後、２．４ＭＰａに加圧しながら、昇温速度３℃／ｍｉｎで３７１℃まで昇温、６０分間保持、徐冷してφ４０ｍｍ厚さ３ｍｍの板を得た。得られた板材を３５７℃条件下で６時間の硬化処理を施した後、所望の寸法に加工し試験片を得た。 (Example 1)
11.1 parts by weight of pitch-based carbon fiber (K223HM manufactured by Mitsubishi Plastics) with an average single fiber length of 200 μm is blended with 100 parts by weight of addition-polymerized polyimide (PET-330 manufactured by Ube Industries Co., Ltd.). It was melt-kneaded at 280 ° C. for 30 minutes under atmospheric pressure. Then, the mixture (bulk molding compound, BMC) cooled to room temperature was obtained. The obtained BMC was divided into easy-to-handle sizes, held in an electric furnace at 310 ° C. for 30 minutes, rapidly cooled and re-pulverized resin mixture (thickened BMC) in a mold for compression molding machines at 280 After melting and soaking by holding at ℃ to 320 ℃ for a certain period of time, pressurizing to 2.4 MPa, raising the temperature to 371 ℃ at a heating rate of 3 ℃ / min, holding for 60 minutes, gradually cooling, φ 40 mm thickness A 3 mm plate was obtained. The obtained plate was subjected to a curing treatment for 6 hours under the condition of 357 ° C., and then processed into a desired dimension to obtain a test piece.
（実施例２）
　付加重合型ポリイミド（宇部興産社製ＰＥＴＩ－３３０）１００重量部に対して、平均単繊維長さ２００μｍのピッチ系炭素繊維（三菱樹脂社製Ｋ２２３ＨＭ）４２．９重量部を配合し、ニーダーにより大気圧下２８０℃、３０分で溶融混練した。その後、室温まで冷却されたＢＭＣを得た。得られたＢＭＣを金型内に納まる大きさ程度に割ってから、ＢＭＣを圧縮成形機用金型内で、２８０℃～３２０℃で一定時間保持することで溶融および均熱した後、１１ＭＰａに加圧しながら、昇温速度３℃／ｍｉｎで３７１℃まで昇温、１時間保持、徐冷してφ１００ｍｍ厚さ３ｍｍの板を得た。得られた板材を３５７℃条件下で６時間の硬化処理を施した後、所望の寸法に加工し試験片を得た。 (Example 2)
42.9 parts by weight of pitch-based carbon fiber (K223HM, manufactured by Mitsubishi Plastics) with an average single fiber length of 200 μm is blended with 100 parts by weight of addition-polymerized polyimide (PET-330, manufactured by Ube Industries). It was melt-kneaded at 280 ° C. for 30 minutes under atmospheric pressure. Thereafter, BMC cooled to room temperature was obtained. After dividing the obtained BMC into a size that fits in the mold, the BMC was held in a mold for a compression molding machine at 280 ° C. to 320 ° C. for a certain period of time, and then melted and soaked. While applying pressure, the plate was heated to 371 ° C. at a rate of temperature increase of 3 ° C./min, held for 1 hour, and gradually cooled to obtain a plate having a diameter of 100 mm and a thickness of 3 mm. The obtained plate was subjected to a curing treatment for 6 hours under the condition of 357 ° C., and then processed into a desired dimension to obtain a test piece.
（実施例３）
　炭素繊維の配合量を１００重量部に変更した以外は実施例２と同じとした。 (Example 3)
The same as Example 2 except that the amount of carbon fiber was changed to 100 parts by weight.
（実施例４）
　電気炉内に３１０℃保持しなかった以外は実施例１と同じとした。得られた樹脂成形体は、反りが生じていたため、表裏層を削って所定の平行度とし、限界ＰＶ値を測定した。削る前の面の限界ＰＶ値は測定していないが、測定した面を観察したところ、削る前の面と比較して炭素繊維が明らかに多く存在していた。このことからも、表面には所定量の炭素繊維が必要であることがわかる。 Example 4
It was the same as Example 1 except that 310 ° C. was not maintained in the electric furnace. Since the obtained resin molding was warped, the front and back layers were scraped to a predetermined parallelism, and the limit PV value was measured. Although the limit PV value of the surface before cutting was not measured, when the measured surface was observed, carbon fibers were clearly present more than the surface before cutting. This also shows that a predetermined amount of carbon fiber is necessary on the surface.
（比較例１）
　炭素繊維を配合しなかった以外は実施例２と同じとした。 (Comparative Example 1)
The same as Example 2 except that no carbon fiber was blended.
（比較例２）
　炭素繊維の配合量を２３３重量部に変更した以外は実施例２と同じとした。なお、溶融混練後に得られたＢＭＣの粘度が高く、賦形工程にて金型内での伸張不足が一部みられ、限界ＰＶ値の測定ができなかった。 (Comparative Example 2)
It was the same as Example 2 except having changed the compounding quantity of carbon fiber into 233 weight part. In addition, the viscosity of the BMC obtained after melt-kneading was high, and in some cases, the elongation in the mold was insufficient in the shaping process, and the limit PV value could not be measured.
　実施例１～４、比較例１、２にて得られた試験片の限界ＰＶ値測定結果、増粘工程の有無、繊維の分散の良否および成形品の欠損の有無を表１に示す。
Figure JPOXMLDOC01-appb-T000001
 Table 1 shows the results of measuring the limit PV values of the test pieces obtained in Examples 1 to 4 and Comparative Examples 1 and 2, the presence or absence of the thickening step, the quality of fiber dispersion, and the presence or absence of defects in the molded product.
Figure JPOXMLDOC01-appb-T000001
（実施例５）
　ＢＭＣを電気炉に３１０℃の条件下で４５分とした以外は実施例１と同じとした。 (Example 5)
Example 1 was the same as Example 1 except that BMC was set in an electric furnace at 310 ° C. for 45 minutes.
（実施例６）
　ＢＭＣを電気炉に３１０℃、６０分とした以外は実施例１と同じとした。 (Example 6)
Example 1 was the same as Example 1 except that BMC was changed to 310 ° C. for 60 minutes in an electric furnace.
（比較例３）
　ＢＭＣを電気炉に３１０℃、１５分とした以外は実施例１と同じとした。なお、金型内からＢＭＣ漏れ、及び繊維の不均一な分布による反り変形が生じた。 (Comparative Example 3)
Example 1 was the same as Example 1 except that BMC was changed to 310 ° C. for 15 minutes in an electric furnace. In addition, warpage deformation due to BMC leakage from the mold and non-uniform fiber distribution occurred.
（比較例４）
　ＢＭＣを電気炉に３１０℃、７５分とした以外は実施例１と同じとした。なお、樹脂粘度が高く伸張せず賦型することができなかった。 (Comparative Example 4)
Example 1 was the same as Example 1 except that BMC was changed to 310 ° C. for 75 minutes in an electric furnace. The resin viscosity was high and it could not be molded without stretching.
　実施例１，５、６、比較例３、４にて得られた試験片の賦形性、繊維の分散の良否、反り／直径比、溶融粘度の測定結果を表２に示す。
Figure JPOXMLDOC01-appb-T000002
 Table 2 shows the measurement results of the shapeability of the test pieces obtained in Examples 1, 5, 6 and Comparative Examples 3, 4, the quality of fiber dispersion, the warp / diameter ratio, and the melt viscosity.
Figure JPOXMLDOC01-appb-T000002
（実施例７）
　付加重合型ポリイミド（宇部興産社製ＰＥＴＩ－３３０）１００重量部に対して、平均単繊維長さ２００μｍのピッチ系炭素繊維（三菱樹脂社製Ｋ２２３ＨＭ）１２．５重量部、グラファイト粉末（和光純薬製０７０－０１３２５）１２．５重量部を配合し、ニーダーにより大気圧下２８０℃、３０分で溶融混練した。その後、室温まで冷却された混合物（バルクモールディングコンパウンド、以下ＢＭＣ）を得た。得られたＢＭＣを金型内に納まる大きさ程度に割ってからＢＭＣを圧縮成形機用金型に、２８０℃～３２０℃で一定時間保持することで溶融および均熱した後、２．４ＭＰａに加圧しながら、昇温速度３℃／ｍｉｎで３７１℃まで昇温、１時間保持、徐冷してφ４０ｍｍ厚さ３ｍｍの板を得た。得られた板材を３５７℃条件下で６時間の硬化処理を施した後、所望の寸法に加工し試験片を得た。 (Example 7)
12.5 parts by weight of pitch-based carbon fiber (K223HM manufactured by Mitsubishi Plastics) with an average single fiber length of 200 μm, graphite powder (Wako Pure Chemical Industries) with respect to 100 parts by weight of addition polymerization type polyimide (PET-330 manufactured by Ube Industries) 070-01325) 12.5 parts by weight were blended and melt kneaded in a kneader at 280 ° C. under atmospheric pressure for 30 minutes. Then, the mixture (bulk molding compound, BMC) cooled to room temperature was obtained. After dividing the obtained BMC into a size that fits in the mold, the BMC was melted and soaked in a mold for a compression molding machine at 280 ° C. to 320 ° C. for a certain period of time, and then 2.4 MPa. While applying pressure, the plate was heated to 371 ° C. at a temperature rising rate of 3 ° C./min, held for 1 hour, and gradually cooled to obtain a plate having a diameter of 40 mm and a thickness of 3 mm. The obtained plate was subjected to a curing treatment for 6 hours under the condition of 357 ° C., and then processed into a desired dimension to obtain a test piece.
（実施例８）
　炭素繊維の配合量を２８．６重量部、グラファイト粉末の配合量を１４．３重量部に変更した以外は実施例７と同じとした。 (Example 8)
Example 7 was the same as Example 7 except that the amount of carbon fiber was changed to 28.6 parts by weight and the amount of graphite powder was changed to 14.3 parts by weight.
（実施例９）
　付加重合型ポリイミド（宇部興産社製ＰＥＴＩ－３３０）１００重量部に対して、平均単繊維長さ２００μｍのピッチ系炭素繊維（三菱樹脂社製Ｋ２２３ＨＭ）２８．６重量部、ＰＴＦＥ粉末（喜多村社製　ＫＴ－６００Ｍ）１４．３重量部を配合し、ニーダーにより大気圧下２８０℃、３０分で溶融混練した。その後、室温まで冷却されたＢＭＣを得た。得られたＢＭＣを金型内に納まる大きさ程度に割ってからＢＭＣを圧縮成形機用金型に、２８０℃～３２０℃で一定時間保持することで溶融および均熱した後、１１ＭＰａに加圧しながら、昇温速度３℃／ｍｉｎで３７１℃まで昇温、１時間保持、徐冷してφ２００ｍｍ厚さ３ｍｍの板を得た。得られた板材を３５７℃条件下で６時間の硬化処理を施した後、所望の寸法に加工し試験片を得た。 Example 9
28.6 parts by weight of pitch-based carbon fiber (K223HM manufactured by Mitsubishi Plastics) with an average single fiber length of 200 μm, PTFE powder (manufactured by Kitamura Co., Ltd.) per 100 parts by weight of addition polymerization type polyimide (PET-330 manufactured by Ube Industries) (KT-600M) 14.3 parts by weight was blended and melt kneaded in a kneader at 280 ° C. under atmospheric pressure for 30 minutes. Thereafter, BMC cooled to room temperature was obtained. After dividing the obtained BMC into a size that fits in the mold, the BMC is melted and soaked in the mold for a compression molding machine at 280 ° C. to 320 ° C. for a certain period of time, and then pressurized to 11 MPa. However, the plate was heated to 371 ° C. at a heating rate of 3 ° C./min, held for 1 hour, and gradually cooled to obtain a plate having a diameter of 200 mm and a thickness of 3 mm. The obtained plate was subjected to a curing treatment for 6 hours under the condition of 357 ° C., and then processed into a desired dimension to obtain a test piece.
（実施例１０）
　炭素繊維の配合量を１４．３重量部、ＰＴＦＥ粉末の配合量を２８．６重量部に変更した以外は実施例９と同じとした。 (Example 10)
Example 9 was the same as Example 9 except that the amount of carbon fiber was changed to 14.3 parts by weight and the amount of PTFE powder was changed to 28.6 parts by weight.
（実施例１１）
　炭素繊維の配合量を３３．３重量部、ＰＴＦＥ粉末の配合量を３３．３重量部に変更した以外は実施例９と同じとした。 (Example 11)
Example 9 was the same as Example 9 except that the amount of carbon fiber was changed to 33.3 parts by weight and the amount of PTFE powder was changed to 33.3 parts by weight.
（比較例５）
　付加重合型ポリイミド（宇部興産社製ＰＥＴＩ－３３０）を２８０℃～３２０℃で一定時間保持することで溶融および均熱した後、１１ＭＰａに加圧しながら、昇温速度３℃／ｍｉｎで３７１℃まで昇温、１時間保持、徐冷してφ１００ｍｍ厚さ３ｍｍの板を得た。得られた板材を３５７℃条件下で６時間の硬化処理を施した後、所望の寸法に加工し試験片を得た。 (Comparative Example 5)
Addition-polymerized polyimide (PET-330 manufactured by Ube Industries, Ltd.) was melted and soaked by holding at 280 ° C to 320 ° C for a certain period of time, and then increased to 371 ° C at a rate of temperature increase of 3 ° C / min while being pressurized to 11 MPa. The temperature was raised, held for 1 hour, and gradually cooled to obtain a plate having a diameter of 100 mm and a thickness of 3 mm. The obtained plate was subjected to a curing treatment for 6 hours under the condition of 357 ° C., and then processed into a desired dimension to obtain a test piece.
　実施例４，７～１１、比較例５にて得られた試験片の限界ＰＶ値測定結果および繊維の分散の良否を表３に示す。 Table 3 shows the results of measurement of limit PV values of the test pieces obtained in Examples 4 and 7 to 11 and Comparative Example 5 and the quality of fiber dispersion.
　１．５ｍｍの板厚さ以外は実施例１２と同じとした試験片における繊維の分散状態を図３に示す。
Figure JPOXMLDOC01-appb-T000003
 FIG. 3 shows the fiber dispersion state in the test piece which was the same as that of Example 12 except for the plate thickness of 1.5 mm.
Figure JPOXMLDOC01-appb-T000003
（実施例１２）
　炭素繊維の配合量を１４．３重量部、グラファイト粉末の配合量を２８．６重量部に変更した以外は実施例６と同じとした。 Example 12
Example 6 was the same as Example 6 except that the amount of carbon fiber was changed to 14.3 parts by weight and the amount of graphite powder was changed to 28.6 parts by weight.
（比較例６）
　炭素繊維の配合量を１６．７重量部、グラファイト粉末の配合量を５０．０重量部に変更した以外は実施例６と同じとした。 (Comparative Example 6)
Example 6 was the same as Example 6 except that the amount of carbon fiber was changed to 16.7 parts by weight and the amount of graphite powder was changed to 50.0 parts by weight.
　実施例４，７～９、１２、比較例６にて得られた試験片の賦形性、繊維の分散の良否、反り／直径比、溶融粘度の測定結果を表４に示す。なお、製品の反りについては、全ての実施例および比較例で、圧縮成形にて板材を得た後、３５７℃条件下で６時間の硬化処理を施す前の状態を測定し、良否判定をおこなった。
Figure JPOXMLDOC01-appb-T000004
 Table 4 shows the measurement results of the formability of the test pieces obtained in Examples 4, 7 to 9, 12 and Comparative Example 6, the quality of fiber dispersion, the warp / diameter ratio, and the melt viscosity. In addition, about the curvature of a product, after obtaining the plate material by compression molding in all the examples and comparative examples, the state before applying the curing treatment for 6 hours under the condition of 357 ° C. is measured, and the quality is determined. It was.
Figure JPOXMLDOC01-appb-T000004
　本発明の樹脂成形体は、限界ＰＶ値が３０００ｋＰａ・ｍ／ｓ以上と摺動性能に優れていることから、自動車、電気・電子分野等の摺動性部材として種々の用途に使用できる。 The resin molded body of the present invention is excellent in sliding performance with a limit PV value of 3000 kPa · m / s or more, and therefore can be used for various applications as a sliding member in automobiles, electrical / electronic fields and the like.

Claims (17)

  1. 　付加反応型ポリイミド樹脂中に機能性繊維が分散して成る樹脂成形体であって、限界ＰＶ値が３０００ｋＰａ・ｍ／ｓ以上であることを特徴とする樹脂成形体。 A resin molded product obtained by dispersing functional fibers in an addition-reaction type polyimide resin, and having a limit PV value of 3000 kPa · m / s or more.
  2. 　前記樹脂成形体を構成する組成物のマトリックスが付加反応型ポリイミド樹脂であり、前記機能性繊維に前記ポリイミド樹脂が含浸している請求項１に記載の樹脂成形体。 The resin molded body according to claim 1, wherein a matrix of the composition constituting the resin molded body is an addition reaction type polyimide resin, and the functional fiber is impregnated with the polyimide resin.
  3. 　前記機能性繊維が、付加反応型ポリイミド１００重量部に対して５～２００重量部の量で含有されている請求項１又は２記載の樹脂成形体。 3. The resin molded body according to claim 1, wherein the functional fiber is contained in an amount of 5 to 200 parts by weight with respect to 100 parts by weight of the addition reaction type polyimide.
  4. 　前記機能性繊維が、炭素繊維、ガラス繊維、アラミド繊維、金属繊維の何れか１種以上である請求項１～３の何れかに記載の樹脂成形体。 The resin molded body according to any one of claims 1 to 3, wherein the functional fiber is at least one of carbon fiber, glass fiber, aramid fiber, and metal fiber.
  5. 　前記機能性繊維が、平均繊維長５０～６０００μｍ、平均繊維径５～２０μｍの炭素繊維である請求項１～４の何れかに記載の樹脂成形体。 5. The resin molded body according to claim 1, wherein the functional fiber is a carbon fiber having an average fiber length of 50 to 6000 μm and an average fiber diameter of 5 to 20 μm.
  6. 　前記付加反応型ポリイミド１００重量部に対して５～４０重量部の量の増粘剤を含有し、該増粘剤が前記樹脂成形体中に分散している請求項１～５の何れかに記載の樹脂成形体。 The thickener is contained in an amount of 5 to 40 parts by weight with respect to 100 parts by weight of the addition reaction type polyimide, and the thickener is dispersed in the resin molded body. The resin molding as described.
  7. 　前記増粘剤が、グラファイト、二硫化モリブデン、ＰＴＦＥ（四フッ化エチレン樹脂）、微細炭素系材料、金属粉の少なくとも１種以上である請求項１～６の何れかに記載の樹脂成形体。 The resin molded body according to any one of claims 1 to 6, wherein the thickener is at least one of graphite, molybdenum disulfide, PTFE (tetrafluoroethylene resin), fine carbon-based material, and metal powder.
  8. 　付加反応型ポリイミド樹脂のプレポリマーと機能性繊維を付加反応型ポリイミド樹脂の融点以上、熱硬化開始温度以下の温度で混練する分散混練工程、
    　該混合物を付加反応型ポリイミド樹脂の熱硬化開始温度以上の温度条件下で賦形する賦形工程、
    を少なくとも有することを特徴とする樹脂成形体の製造方法。     A dispersion kneading step of kneading the prepolymer of the addition reaction type polyimide resin and the functional fiber at a temperature not lower than the melting point of the addition reaction type polyimide resin and not higher than the thermosetting start temperature;
    A shaping step of shaping the mixture under a temperature condition equal to or higher than the thermosetting start temperature of the addition reaction type polyimide resin;
    A method for producing a resin molded product, comprising:
  9. 　前記分散混練工程と賦形工程の間に、分散混練工程で得られた混練物を付加反応型ポリイミド樹脂の熱硬化開始温度以上の温度で一定時間保持することにより混練物の粘度を上昇させる増粘工程を有する請求項８記載の製造方法。 Between the dispersion kneading step and the shaping step, the kneaded product obtained in the dispersion kneading step is increased to increase the viscosity of the kneaded product by holding for a certain time at a temperature equal to or higher than the thermosetting start temperature of the addition reaction type polyimide resin. The manufacturing method of Claim 8 which has a viscous process.
  10. 　前記機能性繊維の含有率が付加反応型ポリイミド１００重量部に対して５～２００重量部である請求項８記載の樹脂成形体の製造方法。 The method for producing a resin molded product according to claim 8, wherein the content of the functional fiber is 5 to 200 parts by weight with respect to 100 parts by weight of the addition reaction type polyimide.
  11. 　前記分散混練工程を経て得られた混合物の３００～３２０℃の温度条件下における溶融粘度が１０～５０００Ｐａ・ｓであり、該混合物を冷却し粉砕混合した後、加圧賦形する請求項８又は１０記載の製造方法。 9. The melt obtained under the temperature condition of 300 to 320 ° C. of the mixture obtained through the dispersion kneading step is 10 to 5000 Pa · s, and the mixture is cooled, pulverized and mixed, and then subjected to pressure shaping. 10. The production method according to 10.
  12. 　前記増粘工程において、混合物の３００～３２０℃の温度条件下における溶融粘度を１０～５０００Ｐａ・ｓに調整する請求項９又は１０記載の製造方法 The method according to claim 9 or 10, wherein in the thickening step, the melt viscosity of the mixture under a temperature condition of 300 to 320 ° C is adjusted to 10 to 5000 Pa · s.
  13. 　前記付加反応型ポリイミド樹脂が、付加反応基としてフェニルエチニル基を有するポリイミド樹脂である請求項８～１２の何れかに記載の製造方法。 The method according to any one of claims 8 to 12, wherein the addition reaction type polyimide resin is a polyimide resin having a phenylethynyl group as an addition reaction group.
  14. 　前記増粘工程おいて、３１０±１０℃の温度で３０～６０分間保持する請求項１３記載の製造方法。 The method according to claim 13, wherein in the thickening step, the temperature is maintained at 310 ± 10 ° C for 30 to 60 minutes.
  15. 　付加反応型ポリイミド１００重量部に対して、５～２００重量部の機能性繊維、５～４０重量部の増粘剤が分散して成る樹脂成形体の製造方法であって、
    　前記付加反応型ポリイミド樹脂のプレポリマー、機能性繊維及び増粘剤を付加反応型ポリイミド樹脂の融点以上、熱硬化開始温度以下の温度で混練する分散混練工程、
    　分散混練工程を経た混合物を付加反応型ポリイミド樹脂の熱硬化開始温度以上の温度条件下で加圧賦形する賦形工程、とから成ることを特徴とする樹脂成形体の製造方法。     A method for producing a resin molded body in which 5 to 200 parts by weight of functional fiber and 5 to 40 parts by weight of a thickener are dispersed with respect to 100 parts by weight of an addition reaction type polyimide,
    A dispersion kneading step of kneading the prepolymer of the addition reaction type polyimide resin, the functional fiber and the thickener at a temperature not lower than the melting point of the addition reaction type polyimide resin and not higher than the thermosetting start temperature,
    And a shaping step of pressure-molding the mixture that has undergone the dispersion kneading step under a temperature condition equal to or higher than the thermosetting start temperature of the addition reaction type polyimide resin.
  16. 　前記分散混練工程を経た混合物の３００～３２０℃の温度条件下における溶融粘度が１０～５０００Ｐａ・ｓである請求項１５記載の製造方法。 The production method according to claim 15, wherein the mixture obtained through the dispersion kneading step has a melt viscosity of 10 to 5000 Pa · s under a temperature condition of 300 to 320 ° C.
  17. 　前記賦形工程が、圧縮成形により行われる請求項８～１６の何れかに記載の製造方法。 The manufacturing method according to any one of claims 8 to 16, wherein the shaping step is performed by compression molding.
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